KR20060113937A - Gas barrier laminate and packaged article, and method for producing gas barrier laminate - Google Patents

Abstract

A gas barrier laminate which has a base material and a layer laminated on at least one surface of the base material, wherein the layer comprises a composition comprising a hydrolysis condensate of at least one compound (L) containing a metal atom having at least one characteristic group selected from a halogen atom and an alkoxy group, bonded thereto, and comprising a neutralized product from a polymer containing at least one functional group selected from a carboxyl group and a carboxylic acid anhydride group, where at least a part of the -COO- group contained in the above at least one functional group is neutralized with a metal ion having a valence of two or more; and a method for producing the above gas barrier laminate. The gas barrier laminate exhibits the high oxygen barrier property which does not depend on humidity, and exhibits the high oxygen barrier property even after it is subjected to a retort treatment, and further is excellent in strength and transparency.

Description

Gas barrier laminate and packaged article, and method for producing gas barrier laminate}

The present invention relates to a gas barrier layered product and a package, and a method for producing the gas barrier layered product.

Packaging materials for packaging foods and various articles often require gas barrier properties, in particular oxygen barrier properties. This is to prevent the effect of oxidative deterioration of the package contents due to oxygen or the like. Especially in the packaging of foods, there exists a problem that microorganisms multiply and the contents decay due to the presence of oxygen. Therefore, in the conventional packaging material, the gas barrier layer which prevents permeation of oxygen is provided and the permeation | transmission of oxygen etc. is prevented.

As such a gas barrier layer, for example, a metal foil, a vapor deposition layer of a metal or a metal compound can be used, and generally an aluminum foil, an aluminum vapor deposition layer, a silicon oxide vapor deposition layer, an aluminum oxide vapor deposition layer, etc. are used. However, a metal layer such as aluminum foil or an aluminum vapor deposition layer has drawbacks such as invisible packaging contents and poor wasteability. Moreover, metal compound layers, such as a silicon oxide vapor deposition layer and an aluminum oxide vapor deposition layer, have the drawback that the gas barrier property falls remarkably due to deformation | transformation of a packaging material, a fall, shock at the time of transport, etc.

In addition, a layer made of a vinyl alcohol polymer having excellent gas barrier properties such as polyvinyl alcohol and an ethylene-vinyl alcohol copolymer may be used as the gas barrier layer. Since the layer which consists of these vinyl alcohol polymers is transparent, and there exists an advantage that there is little problem in the waste surface, the use range is expanded.

The vinyl alcohol polymer is crystallized by hydrogen bonding of hydroxyl groups in the molecule to exhibit gas barrier properties. Therefore, the conventional vinyl alcohol polymer exhibits high gas barrier properties in a dried state, but in the state of moisture absorption under the influence of water vapor or the like, hydrogen bonding is relaxed and gas barrier properties tend to be lowered. Therefore, in vinyl alcohol polymers, such as polyvinyl alcohol, it is difficult to exhibit high gas barrier property under high humidity.

Moreover, as a gas barrier material, the material containing the hydrolysis-condensation product of a metal alkoxide (for example, tetramethoxysilane), and a high molecular compound is studied. For example, Unexamined-Japanese-Patent No. 2002-326303, No. 7-118543, 2000-233478.

In recent years, retort foods which have been sterilized by immersing in hot water after filling the contents with food packaging materials have increased. In such a situation, the retort food packaging material such as bag breaking strength when the content-packed food packaging material falls, oxygen barrier properties after sterilization in hot water, and oxygen barrier property under high humidity until reaching the consumer is required. The level of performance is getting higher. In particular, packaging materials that exhibit high oxygen barrier properties without relying on humidity, high oxygen barrier properties after retort treatment, and excellent strength and transparency are required. Could not be satisfied.

Disclosure of the Invention

In view of such a situation, the present invention provides a gas barrier layered product that exhibits high oxygen barrier properties without relying on humidity, high oxygen barrier properties even after retort treatment, and is excellent in strength and transparency. One of the purposes. In addition, one object of the present invention is to provide a method for industrially advantageously producing such a gas barrier layered product.

MEANS TO SOLVE THE PROBLEM This inventor earnestly examined to achieve the said objective. As a result, a bivalent or higher metal ion containing a laminate having as a gas barrier layer a layer comprising a composition containing a hydrolytic condensate of a metal alkoxide and a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group It was found that the properties of the layer made of the composition were remarkably improved by immersing in a solution to neutralize the functional groups described above in the polymer. As a result of further review, the present invention was completed.

That is, in the gas barrier layered product of the present invention, the gas barrier layered product comprising a substrate and a layer laminated on at least one side of the substrate, wherein the layer is bonded to at least one characteristic group selected from a halogen atom and an alkoxy group. A composition containing a hydrolysis condensate of at least one compound (L) containing a substituted metal atom and a neutralized product of a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group, and containing at least one functional group. At least a part of the -COO- group, characterized in that is neutralized with divalent or more metal ions.

In addition, the package of the present invention is a package using the gas barrier layered product of the present invention.

In addition, the method of the present invention for producing a gas barrier layered product comprises a hydrolysis condensate of at least one compound (L) containing a metal atom bonded to at least one characteristic group selected from a halogen atom and an alkoxy group, and a carboxyl group And a first step of forming a layer comprising a composition containing a polymer containing at least one functional group selected from a carboxylic acid anhydride group on a substrate, and a second step of contacting the layer with a solution containing divalent or more metal ions. Characterized in that.

According to the present invention, there is obtained a gas barrier layered product that exhibits high oxygen barrier properties without depending on humidity, high oxygen barrier properties even after retort treatment, and is excellent in strength and transparency. In the gas barrier layered product of the present invention, the oxygen permeation rate can be set to 1.Ocm ³ / m ² .day · atm or less in an atmosphere of 20 ° C. and 85% RH. Such a gas barrier layered product can be easily produced industrially according to the production method of the present invention. Such a gas barrier layered product is effectively used as a packaging material for food, medicine, medical equipment, machine parts, clothing, and the like, and is particularly effective for food packaging applications that require gas barrier properties under high humidity conditions.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described. In addition, although the specific compound may be illustrated as a substance which expresses a specific function in the following description, this invention is not limited to this. In addition, the material illustrated can be used individually or in combination unless there is a special description.

(Gas barrier layered product)

The gas barrier layered product of the present invention includes a substrate and a layer laminated on at least one side of the substrate. The layer (hereinafter sometimes referred to as a "gas barrier layer") is a hydrolytic condensate of at least one compound (L) containing a metal atom bonded to at least one characteristic group (atomic group) selected from a halogen atom and an alkoxy group And a neutralized product of a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group. At least a part of the -COO- group contained in the at least one functional group is neutralized with a divalent or higher metal ion. In other words, at least some of the at least one functional group together with the divalent or more metal ions constitute a salt.

(Hydrolysis condensate)

At least one of compound (A) and / or compound (B) described below may be applied to compound (L). Hereinafter, a compound (A) and a compound (B) are demonstrated.

Compound (A) is one or more compounds of formula (I) described below.

In Formula I above,

M ¹ is an atom selected from Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La and Nd.

M ¹ is preferably Si, Al, Ti or Zr, particularly preferably Si. In formula (I), R ¹ is an alkyl group such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, and preferably methyl group or ethyl group. In the formula (I), X ¹ is a halogen atom. As a halogen atom of X <^1> , a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example, A chlorine atom is preferable. In addition, in formula (I), Z ¹ is an alkyl group substituted with a functional group having reactivity with a carboxyl group. Here, as a functional group which has the reactivity with a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a halogen atom, a mercapto group, an isocyanate group, a fluoride group, an oxazoline group, or a carbodiimide group, etc. are mentioned, Epoxy group, an amino group, and an isocyanate Groups, ureide groups or halogen atoms are preferred, for example one or more selected from epoxy groups, amino groups and isocyanate groups. Examples of the alkyl group substituted with such a functional group include those described above. In addition, m in the formula (I) is equivalent to the valence of the metal element M ¹ . N in formula (I) is an integer from 0 to (m-1). In formula (I), k is an integer of 0 to (m-1), and 1 ≦ n + k ≦ (m-1).

Specific examples of the compound (A) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrichlorosilane, γ-aminopropyltrimethoxysilane and γ- Aminopropyltriethoxysilane, γ-aminopropyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltrichlorosilane, γ-bromopropyltrimethoxysilane , γ-bromopropyltriethoxysilane, γ-bromopropyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrichlorosilane, γ -Isocyanate propyl trimethoxysilane, (gamma) -isocyanate propyl triethoxysilane, (gamma) -isocyanate propyl trichlorosilane, (gamma) -urade propyl trimethoxysilane, (gamma) -urade propyl triethoxysilane, (gamma) -uraid A piltrichlorosilane, etc. are mentioned. As preferable compound (A), (gamma)-glycidoxy propyl trimethoxysilane, (gamma)-glycidoxy propyl triethoxysilane, (gamma)-chloropropyl trimethoxysilane, (gamma)-chloropropyl triethoxysilane, (gamma)-aminopropyl Trimethoxysilane and (gamma) -aminopropyl triethoxysilane are mentioned.

In addition, compound (B) is one or more types of compound of the following general formula (II).

In Formula II above,

M ² is an atom selected from Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La and Nd, Preferably it is Si, Al, Ti or Zr, Especially preferably, it is Si, Al or Ti. In formula (II), R ² is an alkyl group such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, but is preferably methyl group or ethyl group. In the formula (II), X ² is a halogen atom. Examples of the halogen atom of X ² include a chlorine atom, a bromine atom, an iodine atom and the like, but a chlorine atom is preferable. In the formula (II), R ³ is an alkyl group, an aralkyl group, an aryl group or an alkenyl group. As an alkyl group of R <^3> , a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert- butyl group, n-octyl group, etc. are mentioned, for example. Moreover, as an aralkyl group of R <^3> , a benzyl group, a phenethyl group, a trityl group, etc. are mentioned. Moreover, as an aryl group of R <^3> , a phenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, etc. are mentioned. Moreover, a vinyl group, an allyl group, etc. are mentioned as an alkenyl group of R <^3> . In formula (II), p is equivalent to the valence of the metal element M ² . Q in formula (II) is an integer from 0 to p. In formula (II), r is an integer of 0 to p, where 1 ≦ q + r ≦ p.

In Formula I and Formula II, M ¹ and M ² may be the same or different. In addition, R ¹ and R ² may be the same or different.

Specific examples of the compound (B) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane and vinyltrie. Silicone alkoxides such as methoxysilane, chlorotrimethoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane and trichloroethoxysilane; Halogenated silanes such as vinyltrichlorosilane, tetrachlorosilane and tetrabromosilane; Alkoxytitanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium and methyltriisopropoxytitanium; Titanium halides such as tetrachlorotitanium; Alkoxyaluminum compounds of trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, methyldiisopropoxyaluminum, tributoxyaluminum, diethoxyaluminum chloride; Alkoxy zirconium compounds, such as tetraethoxy zirconium, tetraisopropoxy zirconium, and methyl triisopropoxy zirconium, etc. are mentioned.

The composition which comprises the gas barrier layer of the gas barrier layered product of this invention contains the hydrolysis-condensation product of compound (L). By hydrolyzing the compound (L), at least a part of the halogen and alkoxy groups of the compound (L) is substituted with a hydroxyl group. In addition, the hydrolyzate thereof is condensed to form a compound in which a metal element is bonded via oxygen. When this condensation is repeated, it becomes a compound which is substantially regarded as a metal oxide. Here, in order for such hydrolysis condensation to occur, it is important that a halogen atom or an alkoxy group is bonded to the metal, and when the halogen atom or the alkoxy group is not bonded, the hydrolysis condensation reaction does not occur or is very gentle, thereby obtaining the effect of the present invention. It is difficult to do.

The hydrolysis condensate of the compound (L) included in the gas barrier layer preferably has a condensation degree P of 65 to 99%, more preferably 70 to 99%, further preferably 75 to 99%, as defined below. desirable. Condensation degree P (%) in the hydrolysis-condensation product of compound (L) is computed as follows.

Compound (L) whose total number of alkoxy groups and halogen atoms in one molecule of compound (L) is a, and the sum of the alkoxy groups and halogen atoms condensed in the hydrolysis condensate of the compound (L) is i (units) When the ratio of is yi (%) in the total compound (L), [(i / a) × yi] is calculated for each value of i being an integer of 1 to a (including 1 and a), Add these. That is, the condensation degree P (%) is defined by the following equation.

Said value of yi can be measured with solid NMR (DD / MAS method) etc. regarding the hydrolysis-condensation product of the compound (L) in a gas barrier layer.

The hydrolyzed condensate may be a compound (L), a compound (L) partially hydrolyzed, a compound (L) fully hydrolyzed, a compound (L) partially hydrolyzed or condensed, a compound ( L) is completely hydrolyzed and a part thereof is condensed, or a combination thereof is used as a raw material, and can be produced, for example, by a method used in a known sol-gel method. These raw materials can be manufactured by a well-known method, and what is marketed can be used. Although there is no particular limitation, For example, the condensate obtained by hydrolyzing and condensing about 2-10 molecules can be used as a raw material. Specifically, for example, tetramethoxysilane may be hydrolyzed and condensed to form a linear condensate of 2 to 10 monomers, and the like.

The number of molecules condensed in the hydrolysis condensate of the compound (L) in the composition constituting the gas barrier layer is controlled by the amount of water used in the hydrolysis condensation, the type and concentration of the catalyst, the temperature at which the hydrolysis condensation is performed, and the like. can do.

Although there is no restriction | limiting in particular in the manufacturing method of the hydrolysis-condensation product of compound (L). In a typical example of the sol-gel method, hydrolysis and condensation are performed by adding water, an acid, and an alcohol to the said raw material.

In the following, the compound (L) may be described as a metal alkoxide (a compound containing a metal having an alkoxy group bonded thereto). Instead of the metal alkoxide, a compound containing a metal having a halogen bond can be used.

Compound (L) may be one or more of Compound (A) and / or Compound (B) as described above. When compound (L) contains only compound (A), or contains both compound (A) and compound (B), since the gas barrier property of a gas barrier layered product becomes favorable, it is preferable. And it is more preferable that compound (L) consists of both compound (A) and compound (B) substantially, and the molar ratio of compound (A) / compound (B) exists in the range of 0.5 / 99.5-40 / 60. desirable. In the case where the compound (A) and the compound (B) are used in combination at such a ratio, the gas barrier layered product has excellent performances such as mechanical properties such as gas barrier properties, tensile strength, elongation, appearance, handleability, and the like. The molar ratio of compound (A) / compound (B) is more preferably in the range of 3/97 to 40/60, still more preferably in the range of 4/96 to 30/70.

In another embodiment of the present invention, an organic group having at least one characteristic group selected from a halogen atom, a mercapto group and a hydroxyl group may be further bonded to the metal atom of the compound (L). Hereinafter, the compound (L) to which such organic group is couple | bonded may be called compound (L '). According to this configuration, a laminate having particularly good appearance on the surface is obtained.

As the metal atom of the compound (L '), for example, silicon, tin and titanium can be used. In addition, although a silicon atom may be classified as a nonmetallic element, it is treated as a metal element in this specification. Of these, silicon atoms are preferred in that the reaction is easy to control and a stable product is obtained and is readily available. The silicon atom is bonded to an organic group having at least one characteristic group selected from halogen atoms, mercapto groups and hydroxyl groups, and at least one characteristic group selected from halogen atoms and alkoxy groups. As long as the effect of the present invention is obtained, other substituents may be bonded to the silicon atom. As such another substituent, a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and an amino group are mentioned, for example. As a compound (L ') containing a silicon atom, it is a compound of the following general formula (I'), an allyl (chloropropyl) dichlorosilane, bis (chloromethyl dimethyl siloxy) benzene, and N- (3-triethoxy, for example. Silylpropyl) gluconamide and N- (3-triethoxysilylpropyl) -4-hydroxybutylamide.

Compound (L ') may contain at least one compound (A') of the general formula (I ').

In Formula I 'above,

R ¹ and R ⁴ are each independently an alkyl group,

X ¹ is a halogen atom,

Z ² is an organic group having at least one characteristic group selected from a halogen atom, a mercapto group and a hydroxyl group,

s is an integer from 0 to 3,

t is an integer from 0 to 2,

u is an integer from 0 to 3,

1 ≤ s + u ≤ 3,

1 ≦ s + t + u ≦ 3.

R ¹ and R ⁴ are each independently an alkyl group such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, and preferably methyl group or ethyl group. Examples of the halogen of X ¹ include chlorine, bromine, iodine and the like, and preferably chlorine.

The organic group Z ² may be a hydrocarbon group (eg, having 1 to 5 carbon atoms) substituted with one or more characteristic groups selected from halogen atoms, mercapto groups, isocyanate groups, ureide groups, and hydroxyl groups. As such an organic group, the organic group which changed the chloromethyl group, the chloroethyl group, the chloropropyl group, the chloroethylmethyl group, or these chloro groups into a bromo group, an iodine group, a fluorine group, a mercapto group, or a hydroxyl group is mentioned, for example. In addition, the organic group Z ² may be an organic group having one or more characteristic groups selected from halogen atoms, mercapto groups and hydroxyl groups, and an amide structure.

Specific examples of the compound (A ') in which t is 1 or 2 in formula (I') include, for example, chloromethyl methyldimethoxysilane, chloromethyl dimethylmethoxysilane, 2-chloroethylmethyl dimethoxysilane, 2-chloroethyl Dimethylmethoxysilane, 3-chloropropyl methyldimethoxysilane, 3-chloropropyl dimethylmethoxysilane, mercaptomethyl methyldimethoxysilane, mercaptomethyl dimethylmethoxysilane, 2-mercaptoethylmethyl dimethoxysilane, 2 -Mercaptoethyl dimethylmethoxysilane, 3-mercaptopropylmethyl dimethoxysilane, 3-mercaptopropyl dimethylmethoxysilane, and bis (chloromethyl) methylchlorosilane are mentioned. Moreover, the compound which used the alkoxy group and chlorine groups, such as an ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, can be used for the part of the methoxy group of these compounds.

Specific examples of the compound (A ') in which t is 0 in the formula (I') include, for example, chloro methyltrimethoxysilane, 2-chloroethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 2-chloropropyl Trimethoxysilane, 4-chlorobutyltrimethoxysilane, 5-chloropentyltrimethoxysilane, 6-chlorohexyltrimethoxysilane, (dichloromethyl) dimethoxysilane, (dichloroethyl) dimethoxysilane, (dichloro Propyl) dimethoxysilane, (trichloromethyl) methoxysilane, (trichloroethyl) methoxysilane, (trichloropropyl) methoxysilane, mercaptomethyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane , 3-mercaptopropyltrimethoxysilane, 2-mercaptopropyltrimethoxysilane, 4-mercaptobutyltrimethoxysilane, 5-mercaptopentyltrimethoxysilane, 6-mercaptohexyltrimethoxysilane, (Dimercaptomethyl) dimethoxysilane, (dimercaptoethyl) dimethoxysilane, (dimercaptope Phil) dimethoxysilane, (trimercaptomethyl) methoxysilane, (trimercaptoethyl) methoxysilane, (trimercaptopropyl) methoxysilane, fluoromethyltrimethoxysilane, 2-fluoroethyltrimethoxysilane , 3-fluoropropyltrimethoxysilane, bromomethyltrimethoxysilane, 2-bromoethyltrimethoxysilane, 3-bromopropyltrimethoxysilane, iodomethyltrimethoxysilane, 2-io Doethyltrimethoxysilane, 3-iodopropyltrimethoxysilane, (chloromethyl) phenyltrimethoxysilane, (chloromethyl) phenylethyltrimethoxysilane, 1-chloroethyltrimethoxysilane, 2- ( Chloromethyl) allyltrimethoxysilane, (3-chlorocyclohexyl) trimethoxysilane, (4-chlorocyclohexyl) trimethoxysilane, (mercaptomethyl) phenyltrimethoxysilane, (mercaptomethyl) phenyl Ethyltrimethoxysilane, 1-mercaptoethyltrimethoxysilane, 2- (mercaptomethyl) allyltrimethoxysilane, (3-mercaptocyclohexyl) trimethoxysilane, (4-mercaptocyclohexyl) trimethoxysilane, N- (3-triethoxysilylpropyl) gluconamide, N- (3-triethoxysilyl Propyl) -4-hydroxybutylamide. Moreover, the compound which made the methoxy group of these compounds the alkoxy group and chlorine groups, such as an ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, and tert-butoxy group, can be used.

Compound (L ') is chloromethyltrimethoxysilane, chloromethyltriethoxysilane, chloromethyltrichlorosilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 2-chloroethyltrichloro Silane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltrichlorosilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltrichlorosilane , 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrichlorosilane, (chloromethyl) phenyltrimethoxysilane, (chloromethyl) phenyltriethoxysilane, (chloromethyl) phenyltrichlorosilane, (chloromethyl) phenylethyltrimethoxysilane, ( Chloromethyl) phenylethyltriethoxysilane, (chlorometh ) Phenylethyltrichlorosilane, (mercaptomethyl) phenyltrimethoxysilane, (mercaptomethyl) phenyltriethoxysilane, (mercaptomethyl) phenyltrichlorosilane, (mercaptomethyl) phenylethyltrimethoxysilane , (Mercaptomethyl) phenylethyltriethoxysilane, (mercaptomethyl) phenylethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxypropyltrimethoxysilane, N- From (hydroxyethyl) -N-methylaminopropyltrimethoxysilane, N- (3-triethoxysilylpropyl) gluconamide and N- (3-triethoxysilylpropyl) -4-hydroxybutylamide It is preferred to include at least one compound selected.

Among them, the compound (L ') is chloromethyltrialkoxysilane, chloromethyltrichlorosilane, 2-chloroethyltrialkoxysilane, 2-chloroethyltrichlorosilane, 3-chloropropyltrialkoxysilane, 3-chloropropyltrichloro Rosilane, mercaptomethyltrialkoxysilane, mercaptomethyltrichlorosilane, 2-mercaptoethyltrialkoxysilane, 2-mercaptoethyltrichlorosilane, 3-mercaptopropyltrialkoxysilane, 3-mercaptopropyltrichloro It is preferred to include at least one compound selected from rosilane, N- (3-trialkoxysilylpropyl) gluconamide and N- (3-trialkoxysilylpropyl) -4-hydroxybutylamide. By using these compounds, a gas barrier layered product excellent in transparency is obtained. As a particularly preferable compound (L '), chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercapto Methyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, and 3-mercaptopropyl triethoxysilane are mentioned. By using these compounds as the compound (L '), a gas barrier layered product having excellent gas barrier properties and transparency is obtained. According to the present invention, a gas barrier layered product having a haze value of 3% or less and excellent transparency can be obtained.

Commercially available ones of these compounds (L ') can be used and can be synthesized by a known method.

In the gas barrier layered product using the compound (L '), the oxygen permeation rate can be set to 1.0 cm ³ / m ² .day · atm or less in an atmosphere of 20 ° C. and 85% RH. In addition, in the gas barrier laminated body of another example, haze value can be 3% or less.

In another embodiment, compound (L) may further comprise one or more compounds (B) of formula (II) above in addition to compound (A ′). In addition, in Formula (I ′) and (II), R ¹ and R ² may be the same or different.

When compound (L) contains compound (A ') and compound (B), the molar ratio of compound (A') / compound (B) is preferably in the range of 0.1 / 99.9 to 40/60, and 0.5 More preferably, it is in the range of /99.5 to 30/70, most preferably in the range of 1/99 to 20/80 (for example, 5/95 to 20/80). By using the compound (A ') and the compound (B) together in such a ratio, the gas barrier layered product which is excellent in performance, such as mechanical properties, external appearance, handleability, such as gas barrier property, tensile strength, and elongation, is obtained.

(Carboxylic acid-containing polymer)

The composition constituting the gas barrier layer contains a neutralization of the polymer containing one or more functional groups selected from carboxyl groups and carboxylic acid anhydride groups. The content rate of the neutralizing agent of a polymer in the said composition is not specifically limited, For example, it can be set as the range of 25 weight%-95 weight%. Neutralization of such polymers may include at least a portion of one or more functional groups as divalent or more metal ions for polymers containing one or more functional groups selected from carboxyl groups and carboxylic anhydride groups (hereinafter sometimes referred to as "carboxylic acid-containing polymers"). It is a polymer obtained by neutralizing. The carboxylic acid containing polymer has two or more carboxyl groups or one or more carboxylic anhydride groups in one molecule of the polymer. Specifically, a polymer containing two or more structural units having one or more carboxyl groups such as acrylic acid units, methacrylic acid units, maleic acid units, and itaconic acid units in one molecule can be used. Moreover, the polymer containing the structural unit which has a structure of carboxylic anhydride, such as a maleic anhydride unit and a phthalic anhydride unit, can be used. The structural unit which has one or more carboxyl groups, and / or the structural unit which has the structure of a carboxylic anhydride (henceforth both may abbreviate as carboxylic acid containing unit (C)) may be contained 1 type, or 2 or more types. .

In addition, by setting the content of the carboxylic acid-containing unit (C) in the total structural units of the carboxylic acid-containing polymer to 10 mol% or more, a gas barrier layered product having good gas barrier properties under high humidity is obtained. It is more preferable that it is 20 mol% or more, It is more preferable that it is 40 mol% or more, It is especially preferable that it is 70 mol% or more. Moreover, when a carboxylic acid containing polymer contains both the structural unit containing one or more carboxyl groups, and the structural unit which has a structure of a carboxylic anhydride, it is good if the sum total of both is the said range.

The structural units other than the carboxylic acid-containing unit (C) which the carboxylic acid-containing polymer may contain are not particularly limited, but methyl acrylate units, methyl methacrylate units, ethyl acrylate units, ethyl methacrylate units, butyl acrylate units, meta Structural units derived from (meth) acrylic acid esters such as butyl acrylate units; Structural units derived from vinyl esters such as vinyl formate units and vinyl acetate units; Styrene units, p-styrenesulfonic acid units; And at least one structural unit selected from structural units derived from olefins such as ethylene units, propylene units and isobutylene units. When the carboxylic acid-containing polymer contains two or more kinds of structural units, the carboxylic acid-containing polymer may be any of the form of an alternating copolymer, the form of a random copolymer, the form of a block copolymer, and the form of a tapered copolymer. It can be one.

Preferred examples of the carboxylic acid-containing polymer include polyacrylic acid, polymethacrylic acid, and poly (acrylic acid / methacrylic acid). The carboxylic acid-containing polymer may be one kind or a mixture of two or more kinds of polymers. For example, one or more polymers selected from polyacrylic acid and polymethacrylic acid can be used. Moreover, as a specific example in the case of containing the other structural unit mentioned above, an ethylene-maleic anhydride copolymer, a styrene-maleic anhydride copolymer, an isobutylene-maleic anhydride alternating copolymer, an ethylene-acrylic acid copolymer, ethylene-acrylic acid And saponified products of ethyl copolymers.

Although the molecular weight of a carboxylic acid containing polymer is not restrict | limited, It is preferable that a number average molecular weight is 5,000 or more, and is 10,000 or more from the point which is excellent in the gas barrier property and the mechanical properties, such as a drop impact strength, of the gas barrier layered product obtained. It is more preferable, and it is still more preferable that it is 20,000 or more. The upper limit of the molecular weight of the carboxylic acid-containing polymer is not particularly limited, but is generally 1,500,000 or less.

In addition, the molecular weight distribution of the carboxylic acid-containing polymer is not particularly limited, but the weight average molecular weight / of the carboxylic acid-containing polymer from the viewpoint of improving the surface appearance such as haze of the gas barrier layered product and the storage stability of the solution (S) described below. The molecular weight distribution represented by the ratio of the number average molecular weight is preferably in the range of 1 to 6, more preferably in the range of 1 to 5, and even more preferably in the range of 1 to 4.

The polymer constituting the gas barrier layer of the gas barrier layered product of the present invention contains at least a part of one or more functional groups (hereinafter sometimes referred to as functional group (F)) selected from the carboxyl group and the carboxylic anhydride group of the carboxylic acid-containing polymer. Obtained by neutralization with more than one metal ion. In other words, such polymers include carboxyl groups neutralized with bivalent or more metal ions.

In the polymer constituting the gas barrier layer, for example, 10 mol% or more (eg, 15 mol% or more) of the -COO- group contained in the functional group (F) is neutralized with divalent or more metal ions. In addition, the carboxylic anhydride group is considered to contain two -COO- groups. That is, when a mol carboxyl group and b mol carboxylic anhydride group exist, the -COO- group contained here is a total of (a + 2b) mol. Preferably the ratio neutralized with the bivalent or more metal ion among -COO- groups contained in the functional group (F) is 20 mol% or more, More preferably, it is 30 mol% or more, More preferably, 40 mol% More than 50 mol% (for example, 60 mol% or more). Although the upper limit of the ratio neutralized by the bivalent or more metal ion among the -COO- groups contained in the functional group (F), there is no restriction | limiting in particular, For example, it can be 95 mol% or less. By neutralizing the carboxyl groups and / or carboxylic anhydride groups in the carboxylic acid-containing polymer with divalent or more metal ions, the gas barrier laminate of the present invention exhibits good gas barrier properties under both dry conditions and high humidity conditions.

The neutralization degree (ionization degree) of the functional group F is measured by the infrared absorption spectrum of the gas barrier layered product by the ATR (total reflection measurement) method, or the gas barrier layer is removed from the gas barrier layered product, and its infrared absorption spectrum is KBr. It can obtain | require by measuring by a method. Junghwajeon peak attributable to C = O stretching vibration of the carboxyl groups or carboxylic acid anhydride groups of (before ionization) is observed in the range of 1600cm ^-1 to 1850cm ^-1, and, neutralization (ionization) C = O stretching vibration of the carboxyl group after the Since is observed in the range of 1500cm ^-1 to 1600cm ^-1 can be evaluated by separating both in the infrared absorption spectrum. Specifically, the ratio can be obtained from the maximum absorbance in each range, and the ionization degree of the polymer constituting the gas barrier layer in the gas barrier layered product can be calculated using a calibration curve prepared in advance. In addition, a calibration curve can be created by measuring an infrared absorption spectrum with respect to the some standard sample from which neutralization degree differs.

It is important that the metal ion which neutralizes the functional group F is bivalent or more. When the functional group (F) is neutralized by the unneutralized or monovalent ions alone described below, a laminate having good gas barrier properties is not obtained. However, when the functional group F is neutralized with a small amount of monovalent ions (cationic) in addition to divalent or higher metal ions, the haze of the gas barrier layered product is reduced, and the appearance of the surface is improved. Thus, this invention includes the case where the functional group (F) of a carboxylic acid containing polymer is neutralized by both a bivalent or more metal ion and monovalent ion. Examples of the divalent or higher metal ions include calcium ions, magnesium ions, divalent iron ions, trivalent iron ions, zinc ions, divalent copper ions, lead ions, divalent mercury ions, barium ions, nickel ions and zirconium. Ions, aluminum ions, titanium ions and the like. For example, as the divalent or more metal ions, one or more ions selected from calcium ions, magnesium ions, barium ions, and zinc ions can be used.

In this invention, it is preferable that 0.1-10 mol% of -CO0-groups contained in the functional group (F) (carboxyl group and / or carboxylic anhydride) of a carboxylic acid containing polymer are neutralized by monovalent ion. However, when the degree of neutralization by monovalent ions is high, the gas barrier property of a gas barrier layered product will fall. The degree of neutralization of the functional group (F) by monovalent ions is more preferably in the range of 0.5 to 5 mol%, more preferably in the range of 0.7 to 3 mol%. Examples of the monovalent ions include ammonium ions, pyridinium ions, sodium ions, potassium ions and lithium ions, and ammonium ions are preferable.

(Inorganic components, etc.)

It is preferable that the content rate of the inorganic component in the composition which comprises a gas barrier layer is the range of 5 to 50 weight% from a viewpoint of the favorable gas barrier property of a gas barrier layered product. The content rate thereof is more preferably in the range of 10 to 45% by weight, still more preferably in the range of 15 to 40% by weight, still more preferably in the range of 25 to 40% by weight. The content rate of the inorganic component in a composition can be computed from the weight of the raw material used when manufacturing the said composition. That is, the compound (L), the compound (L) is partially hydrolyzed, the compound (L) is completely hydrolyzed, the compound (L) is partially hydrolyzed and condensed, and the compound (L) is completely The weight of the metal oxide is calculated by assuming that it is hydrolyzed and a part thereof is condensed or a combination thereof is completely hydrolyzed and condensed to become a metal oxide. Then, the weight of the calculated metal oxide is regarded as the weight of the inorganic component in the composition, and the content of the inorganic component is calculated. In addition, when adding inorganic additives, such as a metal salt, a metal complex, and a metal oxide, as mentioned below, the weight of the added inorganic additive is added as it is to the weight of an inorganic component. When the weight calculation of the metal oxide is explained in more detail, when the compound (A) of the formula (I) is completely hydrolyzed and condensed, the composition formula becomes a compound of M ¹ O _{(n + k) / 2} Z ¹ _mnk . Of these compounds, the portion of M ¹ O _{(n + k) / 2} is a metal oxide. Regarding Z ¹ , the organic component is regarded as not being included in the inorganic component. In addition, when the compound (B) of formula (II) is completely hydrolyzed and condensed, the composition formula becomes a compound of M ² O _{(q + r) / 2} R ³ _pqr . Among them is a part of the _{^{M 2 O (q + r)}} / 2 metal oxide. The weight of such a metal oxide divided by the weight of the component except the volatile components, such as a solvent and the compound which arises in the process of changing the said compound (L) into a metal oxide, from the all components added to the 1st process was made 100 times. A value is content rate (%) of the inorganic component here.

In addition, the composition constituting the gas barrier layer may be carbonate, hydrochloride, nitrate, hydrogen carbonate, sulphate, hydrogen sulphate, phosphate, borate or aluminate, as desired, within the scope of not impairing the effects of the present invention. Inorganic acid metal salts; Organic acid metal salts such as oxalate, acetate, tartarate and stearate; Metal complexes such as acetylacetonate metal complexes such as aluminum acetylacetonate, cyclopentadienyl metal complexes such as titanocene, and cyano metal complexes; Layered clay compounds, crosslinking agents, polyalcohols or other high molecular compounds, plasticizers, antioxidants, ultraviolet absorbers, flame retardants and the like. In addition, the composition constituting the gas barrier layer is a fine powder of a metal oxide prepared by wet hydrolysis condensation of the metal alkoxide; Fine powders of metal oxides prepared by dry hydrolysis condensation or combustion of metal alkoxides; Silica fine powder prepared from water glass, and the like.

The surface appearance of a gas barrier layered product becomes favorable by containing polyalcohols in the composition which comprises a gas barrier layer in the gas barrier layered product of this invention. More specifically, when the gas barrier layered product is produced by containing polyalcohols, cracks are less likely to occur in the gas barrier layer, and a gas barrier layered product having a good surface appearance is obtained.

Such polyalcohols used in the present invention are compounds having two or more hydroxyl groups in a molecule, and include from low molecular weight compounds to high molecular weight compounds. Preferably, polyvinyl alcohol, partial saponified polyvinyl acetate, ethylene-vinyl alcohol copolymer, polyethylene glycol, polysaccharides such as polyhydroxyethyl (meth) acrylate, polysaccharides such as starch, polysaccharide derivatives derived from polysaccharides such as starch High molecular weight compounds, such as these.

It is preferable that the usage-amount of said polyalcohols is the range of the weight ratio of carboxylic acid containing polymer / polyalcohols from 10/90 to 99.5 / 0.5. The weight ratio is more preferably in the range of 30/70 to 99/1, still more preferably 50/50 to 99/1, most preferably 70/30 to 98/2.

In the gas barrier layered product of the present invention, a gas barrier layer made of a composition containing the above-described hydrolysis condensate of the compound (L) and a neutralized product of a carboxyl group-containing polymer is formed on at least one side of the substrate. This gas barrier layer may be formed on only one side of the substrate or on both sides. The laminate in which the gas barrier layers are formed on both sides of the substrate has the advantage of being easy to be post-processed such as bonding other films.

The thickness of the gas barrier layer is not particularly limited, but is preferably in the range of 0.1 µm to 100 µm. When it is thinner than 0.1 micrometer, the gas barrier property of a gas barrier layered product may become inadequate. Moreover, when thicker than 100 micrometers, a crack may easily enter a gas barrier layer at the time of processing, transport, and use of a gas barrier layered product. The thickness of the gas barrier layer is more preferably in the range of 0.1 µm to 50 µm, and more preferably in the range of 0.1 µm to 20 µm.

As a base material which comprises the gas barrier layered product of this invention, the base material which consists of various materials can be used. For example, films, such as a thermoplastic resin film and a thermosetting resin film; Fiber aggregates such as fabrics and papers; wood; The film of predetermined shape which consists of a metal oxide, a metal, etc. can be used. Among them, the thermoplastic resin film is particularly useful as a substrate of the gas barrier layered product used in food packaging materials. In addition, the substrate may include a paper layer. The laminated body for paper containers is obtained by using the base material containing a paper layer. In addition, the substrate may be of a multilayer configuration consisting of a plurality of materials.

As a thermoplastic resin film, For example, Polyolefin resin, such as polyethylene and a polypropylene; Polyester-based resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate and copolymers thereof; Polyamide-based resins such as nylon 6, nylon 66 and nylon 12; Polystyrene, poly (meth) acrylic acid ester, polyacrylonitrile, polyvinyl acetate, polycarbonate, polyallylate, regenerated cellulose, polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, ionomer resin The film which shape | molded etc. are mentioned. As a base material of the laminated body used for a food packaging material, the film which consists of polyethylene, polypropylene, polyethylene tetephthalate, nylon 6, or nylon 66 is preferable.

In addition, the laminate of the present invention may further include an adhesive layer (T) disposed between the substrate and the gas barrier layer. According to such a structure, the adhesiveness of a base material and a gas barrier layer can be improved. The adhesive layer T made of an adhesive resin can be formed by treating the surface of the substrate with a known anchor coating agent or by applying a known adhesive to the surface of the substrate. As a result of examining various adhesive resins, it was found that adhesive resins containing urethane bonds and in which the proportion of nitrogen atoms (nitrogen atoms of urethane bonds) in the whole resin range from 0.5 to 12% by weight are preferable. By using such an adhesive resin, the adhesiveness of a base material and a gas barrier layer can be raised especially. By strongly adhering the substrate and the gas barrier layer through the adhesive layer T, it is possible to suppress the deterioration of gas barrier properties and appearance when the gas barrier layered product of the present invention is processed such as printing or laminate. The content rate of the nitrogen atom (nitrogen atom of the urethane bond) contained in the adhesive resin is more preferably in the range of 2 to 11% by weight, and more preferably in the range of 3 to 8% by weight.

As adhesive resin containing a urethane bond, the two-component reaction type polyurethane adhesive which mixes and reacts a polyisocyanate component and a polyol component is preferable.

As the polyisocyanate component, a polyisocyanate component conventionally used in the production of polyurethane is used, and for example, a polyisocyanate monomer and derivatives thereof are used.

As the polyisocyanate monomer, aliphatic diisocyanates such as hexamethylene diisocyanate can be used. Further, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, dicyclohexyl methane-4,4'-diisocyanate, 1,3- or 1,4-bis (isocyanate methyl) cyclohexane or mixtures thereof Alicyclic diisocyanate, such as these, can be used. In addition, araliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene or mixtures thereof Can be used. In addition, aromatic diisocyanates such as 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthylene diisocyanate, etc. Can be used.

As the derivative of the polyisocyanate monomer, a multimer of polyisocyanate such as a dimer or a trimer of the polyisocyanate monomer described above can be used. Furthermore, modified polyisocyanates such as biuret modified, allophanate modified or oxadiazine trione modified obtained by the reaction of the polyisocyanate monomers with water, polyol or carbon dioxide can be used. have. In addition, polyol adducts and / or polyamine adducts obtained by the reaction of the aforementioned polyisocyanate monomers with polyols and / or polyamines are used.

These polyisocyanate components may be used independently and may use two or more types together. Preferably, derivatives of polyisocyanate monomers are used.

As said polyol component, polyester polyol is used preferably. The polyester polyol contains ester units. An ester unit is a unit containing an ester bond and is formed by reaction of a polybasic acid and / or an alkyl ester thereof with a polyol.

There is no particular limitation to the polybasic acid, but preferably aromatic dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid and / or alkyl esters thereof, glutaric acid, succinic acid, adipic acid, pimelic acid , Subic acid, azelaic acid, sebacic acid, dodecane diacid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentane diacid, 2-methyloctane diacid, Aliphatic dicarboxylic acids and dimer acids such as 3,8-dimethyldecane diacid and 3,7-dimethyldecane diacid are used. In addition, there is no particular limitation on the alkyl ester of the polybasic acid, but preferably, the alkyl ester of the polybasic acid is used.

As the polyol, preferably, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol, 1 , 7-heptanediol, 1,9-nonanediol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, 2-methyl-1,8-octanediol and the like Glycols are used. In addition, triols such as glycerin and trimethylolpropane are also preferably used. Moreover, dimethylol alkanoic acid, such as dimethylol propionic acid and dimethylol butanoic acid, is also used preferably.

The polyester polyol is not particularly limited as long as the polyester unit described above is included. Polyester polyols can be synthesized according to known methods. That is, polyester polyols are obtained by reacting polybasic acids and / or alkyl esters thereof with polyols at 160 to 250 ° C. under an inert gas atmosphere.

As a polyol component, polyester polyol can be used as it is. Moreover, polyurethane polyester polyol can be manufactured by chain extension-reacting polyester polyol with polyisocyanate, and this can be used as a polyol component. In addition, a polyester polyol of high molecular weight can be produced by condensing the polyester polyol, and this can be used as a polyol component. Adhesives having various physical properties are obtained by polymerizing polyester polyols in a chain elongation or condensation reaction to high molecular weight. In addition, when using polyester polyol as it is as a polyol component, it is preferable that the number average molecular weight is 500-3000, for example.

It is preferable to apply | coat a two-component reaction type polyurethane adhesive to a polyisocyanate component and a polyol component, and to adjust it so that solid content concentration may be in the range of 0.5 to 50 weight%, and apply it on a base film. As the organic solvent, esters such as methyl acetate and ethyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene are preferably used. When a large amount of water is contained in these organic solvents, the adhesive force between the base material through the adhesive layer T and the gas barrier layer falls. It is preferable that it is 3000 ppm or less, as for the water content rate (weight ratio) contained in an organic solvent, it is more preferable that it is 2000 ppm or less, and it is still more preferable that it is 1000 ppm or less. In order to lower the amount of water contained in the organic solvent, in addition to using an organic solvent having a small initial water content, it is preferable to operate as avoiding contact with the solvent, the solution and the gas barrier layer and the outside air as much as possible. For example, it is preferable to employ the method of nitrogen-sealing the opening part which minimizes the collection | recovery contact time and contact time with the outside air using the apparatus which can operate externally in a sealed type.

When the moisture contained in the organic solvent exceeds 3000 ppm, the adhesive layer T tends to be nonuniform. In order for the base material and the gas barrier layer to strongly adhere through the adhesive layer T, it is important that the adhesive layer T is uniform. This inventor discovered that the uniformity of the contact bonding layer T can be evaluated by the nonuniformity of the haze value of a gas barrier layered product. According to the method described in Examples, the haze value is measured to obtain a standard deviation, and when the value of three times the standard deviation is in the range of 0 to 2.0, the adhesiveness is increased. This value is more preferably in the range of 0 to 1.5, still more preferably in the range of 0 to 1.0.

The thickness of the gas barrier layered product can be increased by increasing the thickness of the adhesive layer T, but the appearance decreases when the thickness is too thick. It is preferable that the thickness of the contact bonding layer T exists in the range of 0.04 micrometer-0.18 micrometer. According to this structure, the gas barrier property and external appearance can be suppressed from deteriorating when printing, laminating, etc. are performed with respect to the gas barrier layered product of this invention, and also the gas barrier layered product of this invention is used. The drop strength of the packaging material can be increased. The thickness of the adhesive layer T is more preferably in the range of 0.06 µm to 0.16 µm, and more preferably in the range of 0.07 µm to 0.14 µm.

In addition, the laminate of the present invention may include a layer (hereinafter sometimes referred to as an "inorganic layer") made of an inorganic substance between the substrate and the gas barrier layer. The inorganic layer can be formed of an inorganic substance such as an inorganic oxide. The inorganic layer can be formed by a vapor phase film formation method such as a vapor deposition method.

The inorganic substance which comprises an inorganic layer should just have gas barrier property with respect to oxygen, water vapor, etc., Preferably it has transparency. For example, the inorganic layer can be formed of an inorganic oxide such as aluminum oxide, silicon oxide, silicon oxynitride, magnesium oxide, stone oxide or a mixture thereof. Among these, aluminum oxide, silicon oxide, and magnesium oxide can be preferably used from the viewpoint of excellent barrier property against gases such as oxygen and water vapor.

Although the preferable thickness of an inorganic layer changes with kinds of the inorganic oxide which comprises an inorganic layer, it is usually the range of 2 nm-500 nm. It is good to select the thickness in which the gas barrier property and mechanical property of a gas barrier layered product become favorable in such a range. When the thickness of the inorganic layer is less than 2 nm, there is no reproducibility in the expression of barrier properties to gases such as oxygen, water vapor, etc., and sufficient gas barrier properties may not be expressed. When the thickness of the inorganic layer exceeds 500 nm, the gas barrier property tends to be lowered when the gas barrier layered product is stretched or bent. The thickness of the inorganic layer is preferably in the range of 5 to 200 nm, more preferably in the range of 10 to 100 nm.

The inorganic layer can be formed by depositing an inorganic oxide on the substrate. Examples of the formation method include vacuum deposition, sputtering, ion plating, chemical vapor deposition (CVD), and the like. Among these, the vacuum vapor deposition method can be used suitably from a productivity viewpoint. As a heating method at the time of vacuum deposition, any of electron beam heating system, resistance heating system, and induction heating system is preferable. Moreover, in order to improve the adhesiveness of an inorganic layer and a base material, and the density of an inorganic layer, it can deposit using a plasma assist method or an ion beam assist method. Moreover, when depositing in order to raise transparency of an inorganic layer, the reaction vapor deposition method which sprays oxygen gas etc. and generate | occur | produces a reaction can be employ | adopted.

The fine structure of the gas barrier layer is not particularly limited, but when the gas barrier layer has the fine structure described below, excellent gas barrier properties are obtained, and when the gas barrier layered product is elongated, deterioration of gas barrier properties, etc. It is preferable because it is suppressed. As a preferable microstructure, it is a sea island structure which consists of sea phase P and island phase Q. The phase (Q) is a region where the proportion of the hydrolyzed condensate of the compound (L) is higher than that of the phase (P).

It is preferable that the sea phase P and the island phase Q each have a microstructure again. For example, the sea phase (P) is a sea phase (P1) mainly composed of the neutralization of the carboxylic acid-containing polymer, and the island phase (P2) mainly composed of the hydrolysis condensate of the compound (L) to form an island island structure again. can do. In addition, the island phase (Q) can again form a sea island structure composed of a sea phase (Q1) mainly consisting of a neutralization of a carboxylic acid-containing polymer, and a island phase (Q2) mainly consisting of a hydrolysis condensate of the compound (L). . It is preferable that the ratio (volume ratio) of [image (Q2) / resolution (Q1)] in the image (Q) is larger than the ratio of [image (P2) / resolution (P1)] in the image (P). The diameter of the island phase Q is preferably in the range of 30 nm to 1200 nm, more preferably in the range of 50 to 500 nm, still more preferably in the range of 50 nm to 400 nm. The diameters of the phase P2 and the phase Q2 are preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 20 nm or less.

In order to obtain such a structure, it is necessary to take appropriate hydrolytic condensation of the compound (L) prior to the crosslinking reaction of the compound (L) and the carboxylic acid-containing polymer. Therefore, a method such as using an appropriate hydrolysis condensation catalyst that uses a specific compound (L) in an appropriate ratio with the carboxylic acid-containing polymer and hydrolyzes condensation before mixing the compound (L) with the carboxylic acid-containing polymer, or the like Method may be employed.

The gas barrier layered product of the present invention may include other layers (eg, thermoplastic resin films or paper) in addition to the substrate and the gas barrier layer. By adding such another layer, heat sealing property can be provided to a gas barrier layered product, or the mechanical properties of a gas barrier layered product can be improved.

When using a thermoplastic resin film or paper (layer) for a base material, the specific example of the gas barrier layered product of this invention is described below. In addition, in the following specific example, in order to simplify a base material, the description of a "film (layer)" may be abbreviate | omitted and only a material may be described.

The structure of the gas barrier layered product of the present invention is, for example, a gas barrier layer / polyester / polyamide / polyolefin, gas barrier layer / polyester / gas barrier layer / polyamide / polyolefin, polyester / gas barrier layer / Polyamide / polyolefin, gas barrier layer / polyamide / polyester / polyolefin, gas barrier layer / polyamide / gas barrier layer / polyester / polyolefin, polyamide / gas barrier layer / polyester / polyolefin, gas barrier layer / Polyolefin / polyamide / polyolefin, gas barrier layer / polyolefin / gas barrier layer / polyamide / polyolefin, polyolefin / gas barrier layer / polyamide / polyolefin, gas barrier layer / polyolefin / polyolefin, gas barrier layer / polyolefin / gas barrier layer / Polyolefin, polyolefin / gas barrier layer / polyolefin, gas barrier layer / polyester / polyolefin, gas barrier layer / polyester / gas difference Layer / polyolefin, polyester / gas barrier layer / polyolefin, gas barrier layer / polyamide / polyolefin, gas barrier layer / polyamide / gas barrier layer / polyolefin, polyamide / gas barrier layer / polyolefin, gas barrier layer / polyester / Paper, gas barrier layer / polyamide / paper, gas barrier layer / polyolefin / paper, polyethylene (PE) layer / paper layer / PE layer / gas barrier layer / polyethylene terephthalate (PET) layer / PE layer, polyethylene (PE) ) Layer / Paper Layer / PE Layer / Gas Block / Polyamide Layer / PE Layer, PE Layer / Paper Layer / PE Layer / Gas Block / PE, Paper Layer / PE Layer / Gas Block / PET Layer / PE Layer , PE layer / paper layer / gas barrier layer / PE layer, paper layer / gas barrier layer / PET layer / PE layer, paper layer / gas barrier layer / PE layer, gas barrier layer / paper layer / PE layer, gas barrier layer / PET layer / paper layer / PE layer, PE layer / paper layer / PE layer / gas barrier layer / PE layer / hydroxyl group-containing polymer layer, PE layer / paper layer / PE layer / gas barrier layer / PE layer / poly Amide layer, PE layer / species Bilayer / PE layer / gas barrier layer / PE layer / polyester layer. Polypropylene or polyethylene is preferable as a polyolefin from a viewpoint of the heat sealing property, mechanical properties, etc. of a gas barrier layered product, polyethylene terephthalate (PET) is preferable as a polyester, and nylon 6 is preferable as a polyamide. Moreover, as a hydroxyl group containing polymer, an ethylene-vinyl alcohol copolymer is preferable. In addition, another layer, for example, an anchor coating layer or a layer made of an adhesive, can be provided between the layers.

The package of the present invention uses the gas barrier layered product of the present invention. Such a package can be applied to various applications, and is preferably used for applications in which gas blocking such as oxygen gas is required. For example, the package of the present invention is preferably used as a package of retort food. In addition, a paper container can be obtained by using a substrate containing a paper layer.

(Method for producing gas barrier layered product)

Hereinafter, the method for manufacturing the gas barrier layered product of this invention is demonstrated. According to this method, the gas barrier layered product of the present invention can be easily produced. Since the structure of the material and laminated body which are used for the manufacturing method of this invention are the same as that mentioned above, description may be abbreviate | omitted about the overlapping part.

In the production method of the present invention, at least one hydrolyzed condensate of at least one compound (L) containing a metal atom bound to at least one characteristic group selected from a halogen atom and an alkoxy group, and at least one selected from a carboxyl group and a carboxylic anhydride group A layer made of a composition containing a polymer containing a functional group (carboxylic acid containing polymer) is formed on the substrate (first step). In the first step, for example, compound (L), partially hydrolyzed compound (L), completely hydrolyzed compound (L), partially hydrolyzed condensation of compound (L) And a process for producing a solution (S) containing at least one metal element-containing compound and a carboxylic acid-containing polymer selected from those wherein the compound (L) is completely hydrolyzed and a portion thereof is condensed, and the solution (S) is applied to the substrate. And drying to form a layer containing the above-described components. Drying of the solution (S) can be performed by removing the solvent contained in the solution (S).

Moreover, when mixing the compound (L) which is not hydrolytically condensed, and a carboxylic acid containing polymer, both will react and it may become difficult to apply | coat the solution (S). Accordingly, the first step is to form a hydrolysis condensate of the compound (L), to prepare a solution (S) containing the hydrolysis condensate and the carboxylic acid-containing polymer thereof, and apply the solution (S) to the substrate. And drying to form a gas barrier layer.

The metal atom of the compound (L) may be again bonded to an organic group having one or more characteristic groups selected from halogen atoms, mercapto groups and hydroxyl groups. That is, the compound (L) may include the compound (L ') described above. By using the compound (L '), a laminate having particularly good appearance on the surface is obtained.

In addition, in the carboxylic acid-containing polymer contained in the solution (S), as described above, part of the -COO- group contained in the functional group (F) (for example, 0.1 to 10 mol%) may be neutralized by monovalent ions. have.

Subsequently, the layer formed on the substrate is brought into contact with a solution containing divalent or more metal ions (second step. Hereinafter, such a step may be referred to as an ionization step). By the second step, at least a part of the functional group (F) (carboxylic acid and / or carboxylic anhydride) contained in the carboxylic acid-containing polymer in the layer is neutralized with divalent metal ions. At this time, the ratio (ionization degree) which is neutralized by bivalent metal ion can be adjusted by changing conditions, such as temperature of the solution containing metal ion, metal ion concentration, and immersion time in the solution containing metal ion.

The second step can be carried out, for example, by spraying a solution containing divalent or more metal ions onto the formed layer, or immersing the substrate and the layer on the base together in a solution containing divalent or more metal ions. .

In addition, below, the laminated body before an ionization process is called laminated body (A), and the laminated body after ionization process may be called laminated body (B).

Hereinafter, the compound (L), the compound (L) is partially hydrolyzed, the compound (L) is completely hydrolyzed, the compound (L) is partially hydrolyzed and condensed, and the compound (L) is completely One or more metal element-containing compounds selected from those hydrolyzed and partially condensed thereof may be referred to as "compound (L) component". The solution (S) can be manufactured using a compound (L) type component, a carboxylic acid containing polymer, and a solvent. For example, the method of adding and mixing a compound (L) type component in the solvent which melt | dissolved the carboxylic acid containing polymer can be employ | adopted. Moreover, the method of adding and mixing a compound (L) component after adding the compound (A) which is a compound (L) component to the solvent which melt | dissolved the carboxylic acid containing polymer (2) can also be employ | adopted. (3) A method of preparing an oligomer (one kind of hydrolysis-condensation product) from a compound (L) -based component in the presence of a solvent or in the absence of a solvent, and mixing a solution in which a carboxylic acid-containing polymer is dissolved in such oligomer can also be employed. have. In addition, a compound (L) type component and its oligomer can be added to a solvent independently, and can be added to a solvent in the form of the solution which melt | dissolved these.

By using the above-mentioned manufacturing method (3) as a method for producing the solution (S), a gas barrier layered product having particularly high gas barrier property is obtained. Hereinafter, the manufacturing method (3) is explained in more detail.

The production method (3) comprises the steps of preparing a solution by dissolving a carboxylic acid-containing polymer in a solvent (St1), a step (St2) and a step (St1) of preparing an oligomer by hydrolyzing and condensing a compound (L) -based component under specific conditions. And a step (St3) of mixing the solution obtained in the step and the oligomer obtained in the step (St2).

The solvent used for dissolving the carboxylic acid-containing polymer in the step (St1) may be selected according to the kind of the carboxylic acid-containing polymer. For example, water is suitable for water-soluble polymers such as polyacrylic acid and polymethacrylic acid. In the case of a polymer such as an isobutylene-maleic anhydride copolymer or a styrene-maleic anhydride copolymer, water containing an alkaline substance such as ammonia, sodium hydroxide or potassium hydroxide is suitable. In the step (St1), alcohols such as methanol and ethanol, unless dissolution of the carboxylic acid-containing polymer is prevented; Ethers such as tetrahydrofuran, dioxane and trioxane; Ketones such as acetone and methyl ethyl ketone; Glycols such as ethylene glycol and propylene glycol; Glycol derivatives such as methyl cellosolve, ethyl cellosolve and n-butyl cellosolve; glycerin; Acetonitrile, dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane and the like can be used in combination.

In step (St2), it is preferable to hydrolyze and condense the compound (L) component in a reaction system containing the compound (L) component, an acid catalyst, water and, if necessary, an organic solvent to obtain an oligomer. Specifically, the method used by the well-known sol-gel method can be applied. When compound (L) is used as the compound (L) -based component, a gas barrier laminate having higher gas barrier properties is obtained.

As the acid catalyst used in the step (St2), a known acid catalyst can be used, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, maleic acid, and the like. Can be used. Of these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid and butyric acid are particularly preferable. The preferred amount of the acid catalyst in accordance with the type of catalyst used, but different from, the compound (L) component in the range of 1 × 10 ^-5 to 10 mol based on 1 mol of the metal atom and preferably, 1 × 10 ^-4 to It is more preferable that it is the range of 5 mol, and it is still more preferable that it is the range of 5 * 10 <^-4> -1 mol. When the amount of acid catalyst used is in this range, a gas barrier layered product having high gas barrier properties is obtained.

In addition, although the preferable usage-amount of water in a process (St2) differs according to the kind of compound (L) component, it is with respect to 1 mol of the alkoxy groups or halogen atoms of a compound (L) component (when both are mixed). It is preferable that it is the range of 0.05-10 mol, It is more preferable that it is the range of 0.1-4 mol, It is still more preferable that it is the range of 0.2-3 mol. When the amount of water used is in this range, the gas barrier property of the gas barrier layered product obtained is particularly excellent. In the case of using a component containing water such as hydrochloric acid in the step (St2), it is preferable to determine the amount of water to be used in consideration of the amount of water introduced by the component.

In addition, in the reaction system of a process (St2), an organic solvent can be used as needed. The organic solvent used will not be specifically limited if it is a solvent in which a compound (L) type component is melt | dissolved. For example, as the organic solvent, alcohols such as methanol, ethanol, isopropanol and normal propanol are suitably used, and alcohols having the same molecular structure (alkoxy component) as the alkoxy group containing the compound (L) component are more suitable. Is used. Specifically, methanol is preferable for tetramethoxysilane, and ethanol is preferable for tetraethoxysilane. Although the usage-amount of an organic solvent is not specifically limited, It is preferable that the density | concentration of a compound (L) type component is 1-90 weight%, More preferably, it is 10-80 weight%, More preferably, it is 10-60 weight%. .

In the step (St2), the temperature of the reaction system is not necessarily limited when hydrolyzing and condensing the compound (L) component in the reaction system, but is usually in the range of 2 to 100 ° C, preferably 4 to 60 ° C. It is the range of, More preferably, it is the range of 6-50 degreeC. The reaction time differs depending on the reaction conditions such as the amount and kind of catalyst, but is usually in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, and more preferably in the range of 0.1 to 6 hours. In addition, the atmosphere of a reaction system is not necessarily limited, Atmospheres, such as an air atmosphere, a carbon dioxide atmosphere, nitrogen stream, and argon atmosphere, can be employ | adopted.

In the step (St2), the entire amount of the compound (L) component may be added to the reaction system at once, and may be added to the reaction system in small portions several times. In any case, it is preferable that the sum total of the usage-amount of a compound (L) type component satisfy | fills the said suitable range. It is preferable that the oligomer manufactured by the process (St2) has a condensation degree of about 25 to 60% when represented by said condensation degree P.

In step (St3), a solution (S) is prepared by mixing an oligomer derived from a compound (L) component and a solution containing a carboxylic acid-containing polymer. From the viewpoint of the storage stability of the solution (S) and the gas barrier property of the obtained gas barrier layered product, the pH of the solution (S) is preferably in the range of 1.0 to 7.0, more preferably in the range of 1.0 to 6.0, More preferably, it is in the range of 1.5 to 4.0.

The pH of the solution S can be adjusted by a known method, for example, acidic compounds such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, butyric acid, ammonium sulfate, sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine It can adjust by adding basic compounds, such as sodium carbonate and sodium acetate. At this time, if a basic compound which introduces a monovalent cation into the solution is used, the effect of neutralizing a part of the carboxyl group and / or the carboxylic anhydride group of the carboxylic acid-containing polymer with monovalent ions is obtained.

The solution S produced at the process St3 changes state with time, and finally becomes a gel composition. The time until the solution S becomes gel is dependent on the composition of the solution S. In order to stably apply | coat solution S to a base material, it is preferable that solution S stabilizes its viscosity over a long time, and then makes it rise gradually. The solution (S) has a viscosity measured by a Brookfield viscometer (Type B viscometer: 60 rpm) even after standing for 2 days at 25 ° C based on the time when the total amount of the compound (L) component is added. It is preferable to adjust a composition so that it may become / m <^2> or less (more preferably 0.5N * s / m <^2> or less, Especially preferably, 0.2N * s / m <^2> or less). Further, the solution (S) is after allowed to stand at 25 ℃ for 10 days, the viscosity thereof 1N · s / m ² or less (more preferably O.1N · s / m ² or less, and particularly preferably O.05N · It is more preferable to adjust the composition so as to be s / m ² or less). Further, even after the solution S is left at 50 ° C. for 10 days, its viscosity is 1 N · s / m ² or less (more preferably 0.1 N · s / m ² or less, particularly preferably 0.05 N · s / It is more preferable to adjust the composition so as to be m ² or less). When the viscosity of the solution (S) is in the above-mentioned range, the gas barrier property of the gas barrier layered product obtained at the same time with excellent storage stability is often better.

To adjust the viscosity of the solution (S) to be within the above range, for example, by adjusting the concentration of the solid content and the pH, carboxymethylcellulose, starch, bentonite, tragacanth rubber, stearates, alginates, methanol, The method of adding a viscosity modifier, such as ethanol, n-propanol, isopropanol, can be used.

In addition, in order to facilitate the application of the solution S to the substrate, an organic solvent which can be uniformly mixed with the solution S is added to the solution S within a range in which the stability of the solution S is not suppressed. can do. As an organic solvent which can be added, For example, Lower alcohol, such as methanol, ethanol, n-propanol, isopropanol; Ethers such as tetrahydrofuran, dioxane and trioxane; Ketones such as acetone, methyl ethyl ketone, methyl vinyl ketone and methyl isopropyl ketone; Glycols such as ethylene glycol and propylene glycol; Glycol derivatives such as methyl cellosolve, ethyl cellosolve and n-butyl cellosolve; glycerin; Acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, dimethoxyethane and the like.

In addition, the solution (S) may be, if desired, inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogencarbonates, sulfates, hydrogen sulfates, phosphates, borates, and aluminates; Organic acid metal salts such as oxalate, acetate, tartarate and stearate; Metal complexes such as acetylacetonate metal complexes such as aluminum acetylacetonate, cyclopentadienyl metal complexes such as titanocene, and cyano metal complexes; It may contain a layered clay compound, a crosslinking agent, the above-described polyalcohols and other high molecular compounds, plasticizers, antioxidants, ultraviolet absorbers, flame retardants and the like. In addition, the solution (S) is a fine powder of metal oxide prepared by wet hydrolysis polycondensation of the metal alkoxide; Fine powders of metal oxides prepared by dry hydrolysis, polycondensation or combustion of metal alkoxides; Silica fine powder prepared from water glass, and the like.

Moreover, it is preferable that the weight ratio of the carboxylic acid containing polymer / polyalcohols of the quantity of polyalcohols added to the solution (S) is 10/90-99.5 / 0.5. The weight ratio range is more preferably 30/70 to 99/1, still more preferably 50/50 to 99/1, most preferably 70/30 to 98/2.

The solution S produced in the step St3 is applied to at least one side of the substrate. Before applying the solution S, the surface of the substrate may be treated with a known anchor coating, or a known adhesive may be applied to the surface of the substrate. The method of apply | coating solution S to a base material is not specifically limited, A well-known method can be used. As a preferable method, for example, cast method, immersion method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kit coating method, die coating method, metering bar coating method, chamber doctor combination use Coating method, curtain coating method, etc. are mentioned.

After apply | coating solution S on a base material, the laminated body (laminated body (A)) before an ionization process is obtained by removing the solvent contained in solution (S). The removal method of the solvent is not particularly limited and known methods can be applied. Specifically, methods, such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method, can be applied individually or in combination. The drying temperature is not particularly limited as long as it is 15 to 20 ° C or more lower than the flow start temperature of the substrate and 15 to 20 ° C or more lower than the thermal decomposition start temperature of the carboxylic acid-containing polymer. The drying temperature is preferably in the range of 80 to 200 ° C, more preferably in the range of 100 to 180 ° C, and even more preferably in the range of 110 to 180 ° C. Removal of the solvent can be carried out under normal pressure or under reduced pressure.

The gas barrier property of this invention by making the laminated body (A) obtained by the above process contact with the solution containing a bivalent or more metal ion (Hereinafter, it may be called solution MI) (ionization process.) A laminate is obtained. In addition, the ionization process can be performed at any stage as long as the effects of the present invention are not impaired. For example, the ionization process can be carried out before or after processing in the form of a packaging material, and can also be carried out after the contents have been filled and sealed in the packaging material.

The solution MI can be produced by dissolving a compound (polyvalent metal compound) that releases divalent or higher metal ions by dissolution in a solvent. Although water is preferably used as the solvent used when preparing the solution MI, it may be a mixture of water and an organic solvent which can be mixed with water. As such a solvent, Lower alcohol, such as methanol, ethanol, n-propanol, isopropanol; Ethers such as tetrahydrofuran, dioxane and trioxane; Ketones such as acetone, methyl ethyl ketone, methyl vinyl ketone and methyl isopropyl ketone; Glycols such as ethylene glycol and propylene glycol; Glycol derivatives such as methyl cellosolve, ethyl cellosolve and n-butyl cellosolve; glycerin; Organic solvents such as acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane and dimethoxyethane.

As the polyvalent metal compound, a compound which releases the metal ions (ie, divalent or higher metal ions) exemplified for the gas barrier layered product of the present invention can be used. For example, calcium acetate, calcium hydroxide, barium hydroxide, calcium chloride, calcium nitrate, calcium carbonate, magnesium acetate, magnesium hydroxide, magnesium chloride, magnesium carbonate, iron (II) acetate, iron (II) chloride, iron (III) acetate, iron chloride (III), zinc acetate, zinc chloride, copper acetate (II), copper acetate (III), lead acetate, mercury acetate (II), barium acetate, zirconium acetate, barium chloride, barium sulfate, nickel sulfate, lead sulfate, chloride Zirconium, zirconium nitrate, aluminum sulfate, potassium alum [KAl (SO ₄ ) ₂ ], titanium sulfate (IV) and the like can be used. One type of polyvalent metal compound can be used, or can be used in combination of 2 or more type. Preferred polyvalent metal compounds include calcium acetate, calcium hydroxide, magnesium acetate, zinc acetate, and barium acetate. In addition, these polyvalent metal compounds can be used in the form of a hydrate.

The concentration of the polyvalent metal compound in the solution MI is not particularly limited, but is preferably in the range of 5 x 10 ^-4 wt% to 50 wt%, more preferably 1 x 10 ^-2 wt% to 30 wt%. It is a range, More preferably, it is the range of 1 to 20 weight%.

The temperature of the solution MI is not particularly limited when the laminate A is brought into contact with the solution MI. However, the higher the temperature, the faster the ionization rate of the carboxyl group-containing polymer. Preferable temperature is the range of 30-140 degreeC, for example, Preferably it is the range of 40-120 degreeC, More preferably, it is the range of 50-100 degreeC.

It is preferable to bring the laminate A into contact with the solution MI, and then to remove the solvent remaining in the laminate. The removal method of the solvent is not particularly limited, and known methods can be applied. Specifically, drying methods, such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method, can be applied individually or in combination of 2 or more types. The temperature at which the solvent is removed is not particularly limited as long as it is 15 to 20 ° C. or more lower than the flow start temperature of the substrate and 15 to 20 ° C. or more lower than the thermal decomposition start temperature of the carboxylic acid-containing polymer. Drying temperature becomes like this. Preferably it is the range of 40-200 degreeC, More preferably, it is the range of 40-150 degreeC, More preferably, it is the range of 40-100 degreeC. Removal of the solvent can be carried out under either normal pressure or reduced pressure.

In order not to damage the surface appearance of the gas barrier layered product, it is preferable to remove excess polyvalent metal compound adhering to the surface of the layered product before or after the removal of the solvent. As a method of removing a polyvalent metal compound, washing | cleaning using the solvent in which a polyvalent metal compound melt | dissolves is preferable. As the solvent in which the polyvalent metal compound is dissolved, a solvent that can be used for the solution MI can be used, and it is preferable to use the same solvent as the solvent of the solution MI.

The manufacturing method of the present invention may further include a step of heat-treating the layer formed in the first step after the first step and before and / or after the second step at a temperature of 120 to 240 ° C. That is, heat processing can be performed with respect to laminated body (A) or (B). The heat treatment may be carried out at any stage as long as the removal of the solvent of the applied solution S is almost completed, but the appearance of the surface by heat treatment of the laminate (i.e., the laminate A) before the ionization step is performed. This good gas barrier layered product is obtained. The temperature of the heat treatment is preferably in the range of 120 to 240 ° C, more preferably in the range of 130 to 230 ° C, and still more preferably in the range of 150 to 210 ° C. Heat treatment can be performed in air, under nitrogen atmosphere, argon atmosphere, or the like.

Moreover, in the manufacturing method of this invention, ultraviolet-ray can be irradiated to laminated body (A) or (B). Ultraviolet irradiation can be performed any time as long as the removal of the solvent of the applied solution S is almost finished. The method is not particularly limited, and a known method can be applied. It is preferable that it is the range of 170-250 nm, and, as for the wavelength of the ultraviolet-ray to irradiate, it is more preferable that it is the range which is 170-190 nm, and / or the range which is 230-250 nm. In addition, radiation of an electron beam, a gamma ray, etc. can be performed instead of ultraviolet irradiation.

Only one of heat treatment and ultraviolet irradiation can be performed, and both can be used in combination. By performing heat treatment and / or ultraviolet irradiation, the gas barrier performance of a laminated body may be expressed more highly.

In order to arrange | position the adhesive layer T between a base material and a gas barrier layer, when a process (processing with an anchor coating agent or application of an adhesive agent) is performed to the surface of a base material before application | coating of the solution S, 1st process [solution S ) After the application] and before the heat treatment and the second step (ionization step), it is preferable to perform a aging treatment in which the substrate to which the solution S is applied is left at a relatively low temperature for a long time. As for the temperature of a aging process, 30-200 degreeC is preferable, More preferably, it is 30-150 degreeC, More preferably, it is 30-120 degreeC. The time for the aging treatment is preferably in the range of 0.5 to 10 days, more preferably in the range of 1 to 7 days, and even more preferably in the range of 1 to 5 days. By performing this aging treatment, the adhesive force between the substrate and the gas barrier layer is more firm. It is preferable to perform heat treatment (heat treatment at 120 ° C to 240 ° C) again after this aging treatment.

The gas barrier layered product of the present invention has excellent barrier properties against gases such as oxygen, water vapor, carbon dioxide, nitrogen, and the like, and can maintain such excellent barrier properties even after being exposed to high humidity conditions or bending conditions. Moreover, even after performing a retort process, it shows the outstanding gas barrier property. As described above, the gas barrier layered product of the present invention has good gas barrier properties which are not influenced by environmental conditions such as humidity, and shows high gas barrier properties even after being exposed to bending conditions, and thus can be applied to various applications. For example, the gas barrier layered product of the present invention is particularly useful as a food packaging material (particularly a retort food packaging material). In addition, the gas barrier layered product of the present invention can be used as a packaging material for packaging industrial materials such as chemicals such as agrochemicals and medicines, precision materials and clothing.

Although an Example is given to the following and this invention is demonstrated in detail, this invention is not limited by these Examples.

Measurement and evaluation in the following Examples are carried out by the methods (1) to (8) described below. In addition, the abbreviation used in the following description about a measuring method and an evaluation method may be mentioned later. In addition, the measurement result and the evaluation result are described in the table published after description of an Example and a comparative example.

(1) storage stability (Examples 1 to 21 and Comparative Examples 1 to 3)

After preparing the solution (S) used for the formation of the gas barrier layer (in the embodiment of the present invention, after the addition of the compound (L) component to the aqueous solution of polyacrylic acid was completely completed), 2 at 25 ° C Politics for days The viscosity before and after leaving this solution is measured using a Brookfield viscometer (Type B viscometer, rotation speed: 60 rpm). And the increase rate of a viscosity is computed from the viscosity of an initial stage and the viscosity after 2 days. In addition, the measuring method of the storage stability of the solution S of Examples 23-28 is described in Example 23.

(2) oxygen barrier properties

Oxygen permeability is measured about the laminated body which has a predetermined structure using the oxygen permeation amount measuring apparatus ("MOCON OX-TRAN 10/50" by a modern control company). Specifically, the laminate is fixed so that the gas barrier layer faces the oxygen supply side and OPET (another gas barrier layer in Example 11) faces the carrier gas side, and the temperature is 20 ° C., oxygen pressure is 1 atm, and the carrier gas. The oxygen permeability (unit: cm ³ / m ² .day · atm) is measured under the condition of 1 atm. At this time, the humidity adopts three conditions of 65% RH, 85% RH and 95% RH, and makes the oxygen supply side and the carrier gas side the same humidity. In Examples 23 to 28, the humidity is measured as 85% RH.

(3) Oxygen barrier property after retort treatment

Two sheets of laminated bodies (size: 12 cm x 12 cm) having a predetermined structure are produced. Then, two sheets thereof are overlapped so that the gas barrier layer is outward, and then the three sides of the laminate are heat sealed up to 5 mm from their ends. After injecting 80 g of distilled water between the two heat-sealed laminates, the remaining fourth side is heat sealed in the same manner. In this way, a pouch in which distilled water is placed is produced.

Subsequently, the pouch is immersed in an autoclave filled with tap water or ion-exchanged water, and a retort treatment is performed at 120 ° C. for 30 minutes. After the retort treatment, the heating was stopped, and when the internal temperature reached 60 ° C, the pouch was taken out from the autoclave and left for 1 hour in a room humidified at 20 ° C and 85% RH. The heat sealed portion is then cut with scissors and the water attached to the surface of the gas barrier layered product is gently wiped with paper towels. Subsequently, the pouch is left in a humidified room at 20 ° C. and 85% RH for 1 week, and the oxygen barrier property after the retort treatment is evaluated by measuring the oxygen permeability of the obtained laminate.

Oxygen permeability is measured using an oxygen permeation measuring device ("MOCON OX-TRAN10 / 50" manufactured by Modern Control). Specifically, the laminate is fixed so that the gas barrier layer faces the oxygen supply side and PP faces the carrier gas side, the temperature is 20 ° C., the humidity is 85% RH on the oxygen supply side, the humidity is 100% RH on the carrier gas side, and the oxygen pressure 1 Oxygen permeability (unit: cm <^3> / m <^2> .day * atm) is measured on condition of atmospheric | air pressure and carrier gas pressure of 1 atmosphere. In addition, the concentration of calcium metal in tap water for use in the retort treatment is 15 ppm. It is also confirmed that no metal atoms are contained in the ion exchanged water. In addition, in the following Example and the comparative example, a retort process is performed using tap water, unless it uses neatly. The calcium concentration in tap water used for the retort treatment is 15 ppm.

(4) tensile strength and elongation

The 1.5 cm * 1.5 cm sample is cut out from the laminated body produced for the above-mentioned (2) oxygen barrier property evaluation, and tensile strength and elongation are measured by the method based on JISK7127.

(5) drop bag breaking strength

Dropping bag breaking strength is obtained by using the pouch produced for evaluating oxygen barrier property after the retort treatment described above (3). That is, after performing the retort treatment similar to the retort treatment performed by evaluation of said (3) with respect to a pouch, a pouch is taken out from an autoclave, and it is left to stand in a humidified room at 20 degreeC and 85% RH for 1 hour. The pouch is lifted to a height of 1.5 m so that the pouch is parallel to the bottom surface and dropped. The drop is repeated until the pouch ruptures and the water leaks from the inside, and the number of drops until the water leaks is obtained. Ten pouches are prepared for one type of laminate, and the average of the number of ten drops is taken as the value of the drop bag breaking strength.

(6) Surface appearance (Examples 1 to 22 and Comparative Examples 1 to 3)

About the laminated body produced for evaluation of said oxygen barrier property (2), surface conditions, such as transparency and the unevenness | corrugation of a gas barrier layer, are observed by visual observation. In case of transparent and smooth surface, it is `` very good (AA) '', slightly cloudy but there is no problem in practical use, and in case of good surface condition, `` good (A) '', opaque, irregularities, etc. When the surface state is not good, it is determined as "bad B."

(7) Neutralization degree (ionization degree) of carboxyl group by metal ion

About the laminated body produced for the above-mentioned (2) oxygen barrier property evaluation, and (3) the laminated body after the retort process produced for the oxygen barrier property evaluation after a retort process, it is a pre-converted infrared spectrophotometer (Shimatsuse Co., Ltd.). The peak of the C = O stretching vibration contained in a gas barrier layer is observed in the mode of ATR (total reflection measurement) using Isakusho, 8200PC. Peak attributable to C = O stretching vibration of the carboxyl groups of the carboxylic acid-containing polymer before ionization is observed in a range of 1600cm ^-1 to 1850cm ^-1, C = O stretching vibration of the carboxyl group after the ionization has 1500cm ^-1 to 1600cm ^{- It} is observed in the range of ¹ . Then, the ratio is calculated from the maximum absorbance in each range, and the degree of ionization is determined using the ratio and the calibration curve prepared by the following method in advance.

[Creation of calibration curve]

Polyacrylic acid having a number average molecular weight of 150,000 is dissolved in distilled water, and the carboxyl group is neutralized with a predetermined amount of sodium hydroxide. The obtained aqueous solution of the neutralized polyacrylic acid is coated and dried on the substrate so as to have the same thickness as the gas barrier layer of the laminate to be measured for ionization degree. A stretched PET film (Toray) coated on the surface of a two-component anchor coating material (manufactured by Mitsui Takeda Chemical Co., Ltd., Takerak 3210 (trade name) and Takenate A3072 (trade name), hereinafter referred to as AC). Lumira (brand name) made by Kabushiki Kaisha. Thickness 12 mu m. Hereinafter, it may abbreviate as "OPET". In this way, 11 kinds of standard samples (laminates (layers consisting of neutralized polyacrylic acid / AC / OPET)) in which the degree of neutralization of the carboxyl groups differ by 10 mol% from 0 to 100 mol% are produced. About these samples, an infrared absorption spectrum is measured in the mode of ATR (total reflection measurement) using a pre-converted infrared spectrophotometer (8200 PC made from Shimadus Corporation). And, as the two peaks, that is, 1600 ^-1 to the peak observed in the range of 1850cm ^-1 and 1500cm ^-1 to 1600cm ^-1 corresponding to the range of C = O stretching vibration which is included in the layer formed of a neutralized product of a polyacrylic acid The ratio of the maximum value of absorbance to the observed peak is calculated. Then, a calibration curve is prepared using the calculated ratio and the degree of ionization of each standard sample.

(8) inorganic component content rate

The inorganic component content of the gas barrier layer before the ionization treatment is calculated by the above-described method, that is, by calculating the weight of the charged raw material.

(9) Evaluation of appearance change with heating (Examples 14 to 21 and Comparative Example 3)

A 10 cm x 10 cm laminate is produced, and four sides of the laminate are fixed to the wooden frame with heat resistant tape. The stack fixed to the wooden rim is not relaxed but in a tense state. The laminate adhered to the wooden frame is allowed to stand for 5 minutes in a hot air dryer having an internal temperature of 120 ° C. Subsequently, the laminate attached to the wooden frame is taken out from the dryer and allowed to cool for 10 minutes in a room temperature atmosphere, and then the appearance of the laminate is observed. Appearance is evaluated according to the following criteria.

AA: No change in appearance compared to before entering hot air dryer.

A: The appearance defect has generate | occur | produced in the slight part.

B: The appearance defects occurred partially or entirely.

(10) Measurement of peel strength

The laminated body of PET layer / AC layer / barrier layer / adhesive layer (1) / nylon layer / adhesive layer (1) / polypropylene layer structure is produced. This laminate is cut to a width of 15 mm. The T-type peel strength is measured at a tensile rate of 250 mm / min, with the peeling surface between the barrier layer and the adhesive layer (1).

(11) Measurement of haze value (Examples 14 to 21 and Comparative Example 3)

A 10 cm x 10 cm laminate is produced, and nine points are equally selected in the laminate, and the haze value of each point is measured. HR-100, manufactured by Murakamishiki Igi Jutsugenkyu Sho, is used for the haze measurement device. In addition, a haze value is measured according to the predetermined measuring method (ASTM D1003-61). A standard deviation is calculated from the measured values of nine points obtained.

(12) Observation of the microstructure of the gas barrier layer

The slice of a laminated body is coat | covered with an epoxy resin, and a very thin slice is produced using the apparatus (Reichert ULTRACUT-S) made from Leica. These sections are observed using a transmission electron microscope (H-800NA type) manufactured by Hitachi Seisakusho Co., Ltd.

(13) Storage Stability (Examples 23-28)

After producing the solution (S) used for formation of a gas barrier layer, after completion | finish of addition of the compound (L) type component to the aqueous solution of polyacrylic acid specifically, it is left still at 25 degreeC. Then, the number of days after which such a solution does not flow completely is measured.

(14) Surface Appearance (Examples 23 to 28)

About the laminated body produced for said (2) oxygen barrier property evaluation, haze value is measured based on JISK7105 method using a haze meter (HR-100, Murakami Sekisai Jutsugen Kyusho, HR-100).

Haze value ((diffuse light transmittance / total light transmittance) x 100) is used as a representative index for evaluating the transparency of the material. In general, the smaller the haze value, the higher the transparency of the material. Whether or not the haze value is sufficiently transparent can be said to be sufficiently transparent, since the criterion differs depending on the use. However, if haze value is 3% or less, it can apply suitably also to the use which requires very high transparency.

<Example 1>

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water, and then ammonia water was added to neutralize 1.5 mol% of the carboxyl group of polyacrylic acid, thereby obtaining an aqueous polyacrylic acid solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 68.4 parts by weight of tetramethoxysilane (TMOS) was dissolved in 82.0 parts by weight of methanol, followed by dissolving 13.6 parts by weight of γ-glycidoxypropyltrimethoxysilane, followed by 5.13 parts by weight of distilled water and 0.1 N (0.1 standard). 12.7 parts by weight of hydrochloric acid was added to prepare a sol, which was subjected to hydrolysis and condensation reaction at 10 ° C. for 1 hour while stirring. The obtained sol was diluted with 185 parts by weight of distilled water, and then rapidly added to 634 parts by weight of a 10% by weight aqueous solution of polyacrylic acid under stirring to obtain a solution (S1). The storage stability is evaluated by the above-described method for this solution (S1).

On the other hand, two-component anchor coating agent [AC; Takerak 3210 (trade name) and Takenate A3072 (trade name) made by Mitsui Takeda Chemical Co., Ltd. were stretched PET films [OPET; It is coated on Lumira (trade name) manufactured by Toray Industries, Ltd., and dried to produce a substrate (AC / OPET) having an anchor coating layer. After coating the solution (S1) with a bar coater so that the thickness after drying on the anchor coating layer of this substrate to 2㎛, dried for 5 minutes at 80 ℃, then aged for 3 days (72 hours) at 50 ℃, Again, heat treatment is performed at 200 ° C. for 5 minutes in dry air. In this manner, a laminate (gas barrier layer (2 μm) / AC / OPET (12 μm)) having a gas barrier layer that is colorless and transparent and has a good appearance is obtained (hereinafter, such a laminate is referred to as laminate 1). There is a case.

Then, calcium acetate is dissolved in distilled water so that the concentration is 10% by weight, and this aqueous solution is kept at 80 ° C. And the laminated body 1 obtained above is immersed in such aqueous solution (80 degreeC; MI-1) for about 20 second. After immersion, the laminate was taken out, the surface of the laminate was washed with distilled water adjusted to 80 占 폚 and then dried at 80 占 폚 for 5 minutes to obtain the laminate (B-1) of the present invention. About the said laminated body (B-1), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 60 mol% of the carboxyl groups were neutralized with calcium ions. The oxygen barrier property, surface appearance, tensile strength, elongation, and inorganic component content rate of the laminate (B-1) thus obtained were evaluated by the above-described method.

A 10 cm x 10 cm sample is cut out from the laminate (B-1), and the haze value is measured according to the method described above. Three times the standard deviation of the haze value is 0.20, which is a very good value. In addition, the microstructure of the gas barrier layer is observed by a transmission electron microscope. The gas barrier layer has a sea island structure consisting of sea phase P and island phase Q. The phase (Q) is elliptical, and the diameter in the major axis direction of the ellipse is 50 to 500 nm.

Sea P has a sea island structure composed of sea P1 and island P2. The sea phase (P1) is mainly formed of a neutralized polyacrylic acid, and the island phase (P2) is mainly formed of a hydrolytic condensate of tetramethoxysilane. The diameter of the island phase P2 is about 20 nm or less.

The phase Q has a sea island structure composed of the phase Q1 and the phase Q2. The sea phase (Q1) is mainly formed of a neutralized polyacrylic acid, and the island phase (Q2) is mainly formed of a hydrolysis condensate of tetramethoxysilane. The diameter of island phase Q2 is 20 nm or less. Judging from the images of the electron microscope, the resolution P and the phase Q are composed of the same components, but the phase Q has a higher concentration of hydrolyzed condensates of tetramethoxysilane.

Further, stretched nylon film (manufactured by UNITIKA, Inc., product name), thickness 15 µm, may be abbreviated as "ONy"), and polypropylene film [RXC-18 (manufactured by TOCELLO Corporation) ), And 50 µm thick, sometimes abbreviated as "PP". The two-component adhesives (A-385 (trade name) and A-50 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) were coated and dried, respectively. It is prepared and laminated with the laminate (B-1; gas barrier layer / AC / OPET). In this manner, a laminate (B-1-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP is obtained. Using this laminate, the drop bag breaking strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured. The ionization degree after the retort treatment is 92 mol%, and the oxygen permeability after the retort treatment is very good, less than 0.2 cm ³ / m ² · day · atm.

<Example 2>

First, the laminated body 1 demonstrated in Example 1 is produced. On the other hand, magnesium acetate is dissolved in distilled water so as to have a concentration of 10% by weight to prepare an aqueous solution, and the aqueous solution is kept at 80 ° C. The laminated body 1 is immersed in such aqueous solution (80 degreeC; MI-2) for about 20 second. After immersion, the laminate was taken out, the surface of the laminate was washed with distilled water adjusted to 80 占 폚, and then dried at 80 占 폚 for 5 minutes to obtain the laminate (B-2) of the present invention. About the said laminated body (B-2), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 64 mol% of the carboxyl groups were neutralized with magnesium ions. In addition, the oxygen barrier property, surface appearance, tensile strength, elongation, and inorganic component content rate of a laminated body (B-2) are evaluated by said method.

Further, using the laminate (B-2), a laminate (B-2-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 1. To make. The drop bag breaking strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree after the retort treatment is 88 mol%, and the oxygen permeability after the retort treatment is very good, less than 0.2 cm ³ / m ² · day · atm.

<Example 3>

First, the laminated body 1 demonstrated in Example 1 is produced. On the other hand, zinc acetate is dissolved in distilled water so as to have a concentration of 10% by weight to prepare an aqueous solution, and the aqueous solution is kept at 80 ° C. The laminate 1 is immersed in this aqueous solution (80 ° C; MI-3) for about 20 seconds. After immersion, the laminate was taken out, the surface of the laminate was washed with distilled water adjusted to 80 占 폚, and then dried at 80 占 폚 for 5 minutes to obtain the laminate (B-3) of the present invention. About the said laminated body (B-3), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 60 mol% of the carboxyl groups were neutralized with zinc ions. In addition, the oxygen barrier property, surface appearance, tensile strength, elongation, and inorganic component content rate of a laminated body (B-3) are evaluated by the above-mentioned method.

Further, using the laminate (B-3), a laminate (B-3-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 1. To make. The drop bag breaking strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree after the retort treatment is 90 mol%, and the oxygen permeability after the retort treatment is very good, less than 0.2 cm ³ / m ² · day · atm.

<Example 4>

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 is dissolved in distilled water to obtain a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 68.4 parts by weight of tetramethoxysilane (TMOS) was dissolved in 82.0 parts by weight of methanol, followed by dissolving 13.6 parts by weight of γ-glycidoxypropyltrimethoxysilane, followed by 5.13 parts by weight of distilled water and 12.7 parts by weight of 0.1N hydrochloric acid. Part is added to prepare a sol, which is subjected to hydrolysis and condensation reaction at 10 ° C. for 1 hour while stirring. The obtained sol was diluted in 185 parts by weight of distilled water and then rapidly added to 634 parts by weight of an aqueous 10% by weight polyacrylic acid solution under stirring to obtain a solution (S4). The storage stability is evaluated by the above-described method for this solution (S4).

Subsequently, a laminate 4 having a structure of a gas barrier layer (2 μm) / AC / OPET (12 μm) in the same manner as in Example 1, except that solution S4 was used instead of solution S1. ) In the laminate 4, the gas barrier layer is colorless and transparent, and the appearance of the surface is good.

Next, the laminate 4 is subjected to ionization treatment using calcium acetate aqueous solution (MI-1) under the same conditions as in Example 1. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 ° C., and then dried at 80 ° C. for 5 minutes to obtain a laminate (B-4) of the present invention. About the laminated body (B-4), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 63 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, tensile strength, elongation, and inorganic component content rate of a laminated body (B-4) are evaluated by the above-mentioned method.

In addition, using the laminate (B-4), a laminate (B-4-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 1. To make. The drop bag breaking strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree after the retort treatment is 92 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.2 cm ³ / m ² · day · atm.

Example 5

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 is dissolved in distilled water to obtain a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 60.8 parts by weight of tetramethoxysilane (TMOS) was dissolved in 88.0 parts by weight of methanol, followed by dissolving 27.2 parts by weight of γ-glycidoxypropyltrimethoxysilane, followed by 5.20 parts by weight of distilled water and 12.9 parts by weight of 0.1N hydrochloric acid. Part is added to prepare a sol, which is subjected to hydrolysis and condensation at 1O &lt; 0 &gt; C for 1 hour with stirring. The obtained sol was diluted in 239 parts by weight of distilled water, and then quickly added to 567 parts by weight of an aqueous 10% by weight polyacrylic acid solution under stirring to obtain a solution (S5). The storage stability of this solution (S5) is evaluated by the method described above.

Subsequently, a laminate 5 having a structure of a gas barrier layer (2 μm) / AC / OPET (12 μm) was obtained in the same manner as in Example 1, except that solution S5 was used instead of solution S1. ) In the laminate 5, the gas barrier layer is colorless and transparent, and the appearance of the surface is good.

Next, the laminated body 5 is ionized using calcium acetate aqueous solution (MI-1) on the conditions similar to Example 1. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 占 폚 and then dried at 80 占 폚 for 5 minutes to obtain a laminate (B-5) of the present invention. About the laminated body (B-5), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 55 mol% of the carboxyl groups were neutralized with calcium ions. Moreover, the oxygen barrier property, surface appearance, tensile strength, elongation, and inorganic component content rate of a laminated body (B-5) are evaluated by the above-mentioned method.

In addition, using the laminated body (B-5), the laminated body (B-5-1) which has a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP in the same manner as in Example 1 To make. The drop bag breaking strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree after the retort treatment is 87 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.2 cm ³ / m ² · day · atm.

<Example 6>

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 is dissolved in distilled water to obtain an aqueous polyacrylic acid solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 36.3 parts by weight of γ-glycidoxypropyltrimethoxysilane was dissolved in 36.3 parts by weight of methanol, and then 1.55 parts by weight of distilled water and 3.84 parts by weight of 0.1N hydrochloric acid were added to prepare a sol, which was stirred for 1 hour at 10 ° C. Hydrolysis and condensation reactions are carried out. The obtained sol was diluted in 179 parts by weight of distilled water, and then rapidly added to 743 parts by weight of a 10% by weight aqueous solution of polyacrylic acid under stirring to obtain a solution (S6). The storage stability of this solution (S6) is evaluated by the method described above.

Subsequently, a laminate 6 having a structure of a gas barrier layer (2 μm) / AC / OPET (12 μm) in the same manner as in Example 1, except that solution S6 was used instead of solution S1. ). In the laminate 6, the gas barrier layer is colorless and transparent, and the appearance of the surface is good.

Next, the laminated body 6 is ionized using calcium acetate aqueous solution (MI-1) on the conditions similar to Example 1. FIG. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 ° C. and then dried at 80 ° C. for 5 minutes to obtain a laminate (B-6) of the present invention. About the laminated body (B-6), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 70 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, and inorganic component content rate of a laminated body (B-6) are evaluated by said method.

In addition, using the laminated body (B-6), the laminated body (B-6-1) which has a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP in the same manner as in Example 1 To make. The drop bag breaking strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree after the retort treatment is 95 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.2 cm ³ / m ² · day · atm.

<Example 7>

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 is dissolved in distilled water to obtain a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 45.6 parts by weight of tetramethoxysilane (TMOS) was dissolved in 54.6 parts by weight of methanol, followed by dissolving 9.07 parts by weight of γ-glycidoxypropyltrimethoxysilane, followed by 3.42 parts by weight of distilled water and 8.44 parts of 0.1N hydrochloric acid. A sol is prepared by adding parts by weight and subjected to hydrolysis and condensation reaction at 10 ° C. for 1 hour with stirring. The obtained sol was diluted with 123 parts by weight of distilled water and then rapidly added to 756 parts by weight of a 10% by weight aqueous solution of polyacrylic acid under stirring to obtain a solution (S7). The storage stability of this solution (S7) is evaluated by the method described above.

Subsequently, the laminate 7 having a structure of a gas barrier layer (2 μm) / AC / OPET (12 μm) in the same manner as in Example 1 except that the solution S7 was used instead of the solution S1. To produce. In the laminate 7, the gas barrier layer is colorless and transparent, and the appearance of the surface is good.

Next, the laminated body 7 is ionized using calcium acetate aqueous solution (MI-1) on the conditions similar to Example 1. FIG. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 占 폚 and then dried at 80 占 폚 to obtain the laminate (B-7) of the present invention. About the laminated body (B-7), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 67 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, tensile strength, elongation, and inorganic component content rate of laminated body (B-7) are evaluated by the above-mentioned method.

In addition, using the laminated body (B-7), the laminated body (B-7-1) which has a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP in the same manner as in Example 1 To make. The drop bag breaking strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree after the retort treatment was 93 mol%, and the oxygen permeability after the retort treatment was very good at less than 0.2 cm ³ / m ² · day · atm.

<Example 8>

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 is dissolved in distilled water to obtain a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 68.4 parts by weight of tetramethoxysilane (TMOS) was dissolved in 78.7 parts by weight of methanol, and then 10.3 parts by weight of γ-aminopropyltrimethoxysilane was dissolved, 5.13 parts by weight of distilled water and 12.7 parts by weight of 0.1N hydrochloric acid were added. A sol is prepared and subjected to hydrolysis and condensation reaction at 10 ° C. for 1 hour with stirring. The obtained sol was diluted in 158 parts by weight of distilled water and then quickly added to 667 parts by weight of a 10% by weight aqueous solution of polyacrylic acid under stirring to obtain a solution (S8). The storage stability of the solution (S8) is evaluated by the method described above.

Subsequently, a laminate 8 having a structure of a gas barrier layer (2 μm) / AC / OPET (12 μm) in the same manner as in Example 1, except that solution S8 was used instead of solution S1. ). In the laminate 8, the gas barrier layer is colorless and transparent and has a good appearance.

Next, the laminated body 8 is ionized using calcium acetate aqueous solution (MI-1) on the conditions similar to Example 1. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 ° C., and then dried at 80 ° C. for 5 minutes to obtain a laminate (B-8) of the present invention. About the laminated body (B-8), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 62 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, tensile strength, elongation, and inorganic component content rate of the laminated body (B-8) are evaluated by the above-mentioned method.

In addition, using the laminated body (B-8), a laminated body (B-8-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 1. To make. The drop bag breaking strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree after the retort treatment is 88 mol%, and the oxygen permeability after the retort treatment is very good, less than 0.2 cm ³ / m ² · day · atm.

Example 9

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 and polyvinyl alcohol [Gurarese, PVA-105 (trade name); Viscosity average degree of polymerization 500] is dissolved in distilled water so that the weight ratio is 97: 3. Next, ammonia water is added to neutralize 1.5 mol% of the carboxyl groups of polyacrylic acid. Thus, the polymer aqueous solution which contains 10 weight% of solid content concentration in aqueous solution, and contains polyacrylic acid and polyvinyl alcohol is obtained.

Subsequently, 68.4 parts by weight of tetramethoxysilane (TMOS) was dissolved in 82.0 parts by weight of methanol, followed by dissolving 13.6 parts by weight of γ-glycidoxypropyltrimethoxysilane, followed by 5.13 parts by weight of distilled water and 12.7 parts by weight of 0.1N hydrochloric acid. Part is added to prepare a sol, which is subjected to hydrolysis and condensation reaction at 10 ° C. for 1 hour while stirring. The obtained sol was diluted in 185 parts by weight of distilled water and then quickly added to 634 parts by weight of the aqueous polymer solution under stirring to obtain a solution (S9). The storage stability of this solution (S9) is evaluated by the method described above.

Subsequently, the laminate 9 having a structure of a gas barrier layer (2 μm) / AC / OPET (12 μm) in the same manner as in Example 1 except that the solution (S9) was used instead of the solution (S1). To produce. In the laminate 9, the gas barrier layer is colorless and transparent and has a good appearance.

Next, the laminate 9 is subjected to ionization treatment using calcium acetate aqueous solution (MI-1) under the same conditions as in Example 1. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 ° C., and then dried at 80 ° C. for 5 minutes to obtain a laminate (B-9) of the present invention. About the laminated body (B-9), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 58 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, tensile strength, elongation, and inorganic component content rate of the laminated body (B-9) are evaluated by the above-mentioned method.

In addition, using the laminated body (B-9), a laminated body (B-9-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 1. To make. The drop bag breaking strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree after the retort treatment is 91 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.2 cm ³ / m ² · day · atm.

<Example 10>

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 and starch (soluble starch manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved in distilled water so as to have a weight ratio of 97: 3. Subsequently, ammonia water is added to neutralize 1.5 mol% of the carboxyl groups of polyacrylic acid. Thus, the solid content concentration in aqueous solution is 10 weight%, and the polymer aqueous solution containing polyacrylic acid and starch is obtained.

Subsequently, 68.4 parts by weight of tetramethoxysilane (TMOS) was dissolved in 82.0 parts by weight of methanol, followed by dissolving 13.6 parts by weight of γ-glycidoxypropyltrimethoxysilane, followed by 5.13 parts by weight of distilled water and 12.7 parts by weight of 0.1N hydrochloric acid. Part is added to prepare a sol, which is subjected to hydrolysis and condensation at 1O &lt; 0 &gt; C for 1 hour with stirring. The obtained sol was diluted in 185 parts by weight of distilled water and then rapidly added to 634 parts by weight of the aqueous polymer solution under stirring to obtain a solution (S10). The storage stability of this solution (S10) is evaluated by the method described above.

Subsequently, the laminate 10 having a structure of a gas barrier layer (2 μm) / AC / OPET (12 μm) in the same manner as in Example 1 except that the solution (S10) was used instead of the solution (S1). To produce. The gas barrier layer is colorless and transparent and has a good appearance.

Next, the laminate 10 is subjected to ionization treatment using calcium acetate aqueous solution (MI-1) under the same conditions as in Example 1. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 ° C., and then dried at 80 ° C. for 5 minutes to obtain a laminate (B-10) of the present invention. About the laminated body (B-10), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 57 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, tensile strength, elongation, and inorganic component content rate of a laminated body (B-10) are evaluated by the above-mentioned method.

Further, using the laminate (B-10), a laminate (B-10-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 1. To make. The drop bag breaking strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree after the retort treatment is 92 mol%, and the oxygen permeability after the retort treatment is very good, less than 0.2 cm ³ / m ² · day · atm.

<Example 11>

First, the solution S1 is produced in the same manner as in Example 1. Using this solution (S1), a gas barrier layer is formed on the substrate (OPET) by the following method.

First, a stretched PET film [OPET; Toray Corporation, Lumira (trade name)] two-sided anchor coating agent [AC; Takerak 3210 (trade name) and Takenate A3072 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.] are applied and dried. The solution (S1) is coated on the anchor coating layer by a bar coater so that the thickness after drying is 1 μm, and dried at 80 ° C. for 5 minutes. Next, the same two-component anchor coating agent is applied to the other side of the stretched PET film and dried. The solution (S1) is coated on the anchor coating layer by a bar coater so that the thickness after drying is 1 µm, and dried at 80 ° C for 5 minutes. Subsequently, heat treatment was performed at 200 ° C. for 5 minutes in dry air, and the laminate 11 had a structure of a gas barrier layer (1 μm) / AC / OPET (12 μm) / AC / gas barrier layer (1 μm). ). The gas barrier layer is colorless and transparent and has a good appearance.

Next, the laminate 11 is subjected to ionization treatment using calcium acetate aqueous solution (MI-1) under the same conditions as in Example 1. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 DEG C, and then dried at 80 DEG C for 5 minutes to obtain the laminate (B-11) of the present invention. About the laminated body (B-11), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 61 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, tensile strength, elongation, and inorganic component content rate of laminated body (B-11) are evaluated by the above-mentioned method.

In addition, the laminated body (B-11) which has a structure of a gas barrier layer / AC / OPT / AC / gas barrier layer / adhesive / ONy / adhesive / PP in the same manner as in Example 1 using the laminate (B-11) -11-1). The drop bag breaking strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree of the outermost layer after the retort treatment is 90 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.2 cm ³ / m ² · day · atm.

<Example 12>

First, the laminated body 1 demonstrated in Example 1 is produced. The laminate 1 is subjected to ionization treatment under the same conditions as in Example 1 except that the time for immersing the laminate 1 in the calcium acetate aqueous solution is about 1 second. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 占 폚, and then dried at 80 占 폚 for 5 minutes to obtain a laminate (B-12) of the present invention. About the laminated body (B-12), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 5 mol% of the carboxyl groups were neutralized with calcium ions. The oxygen barrier property, surface appearance, tensile strength, elongation, and inorganic component content rate of the laminate (B-12) thus obtained were evaluated by the above-described method.

In addition, using the laminate (B-12), a laminate (B-12-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 1. To make. The drop bag breaking strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree after the retort treatment is 5 mol%. Oxygen permeability after retort treatment is 60 cm ³ / m ² · day · atm. In this embodiment, the retort treatment is performed using ion-exchanged water.

Example 13

First, the laminated body 1 demonstrated in Example 1 is produced. The laminate 1 was subjected to ionization under the same conditions as in Example 1, except that the time for immersing the laminate 1 in the calcium acetate aqueous solution (MI-1) was changed from 20 seconds to 3 seconds. do. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 占 폚 and further dried at 80 占 폚 for 5 minutes to obtain the laminate (B-13) of the present invention. About the laminated body (B-13), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 15 mol% of the carboxyl groups were neutralized with calcium ions. The oxygen barrier property, surface appearance, tensile strength, elongation, and inorganic component content rate of the laminate (B-13) thus obtained were evaluated by the above-described method.

In addition, using the laminate (B-13), a laminate (B-13-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 1. To make. The drop bag breaking strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree after the retort treatment is 15 mol%. Oxygen permeability after the retort treatment is good at 12 cm ³ / m ² · day · atm. In this embodiment, the retort treatment is performed using ion-exchanged water.

Comparative Example 1

A laminate having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 1, without using the laminate 4 produced in Example 4 without ionization treatment. To make. The drop bag breaking strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The degree of ionization after the retort treatment is O%. The oxygen permeability after the retort treatment is 87 cm ³ / m ² · day · atm, and the characteristics are inferior as compared with the laminate of the examples. In addition, in this comparative example, a retort process is performed using ion-exchange water. Table 2 below also shows the results of evaluating oxygen barrier properties, surface appearance, tensile strength, and inorganic component content of the laminate 4.

Comparative Example 2

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 is dissolved in distilled water to obtain a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, a laminate [polyacrylic acid (2 μm) / AC / OPET (12 μm)] was produced in the same manner as in Example 1 except that a 10% by weight polyacrylic acid aqueous solution was used instead of the solution (S1). . The polyacrylic acid layer is colorless and transparent and has a good appearance.

Then, calcium acetate is dissolved in distilled water so that the concentration is 10% by weight, and this aqueous solution is kept at 80 ° C. And when the said laminated body was immersed in such aqueous solution (80 degreeC), since a part of polyacrylic acid layer melt | dissolves, further evaluation is stopped.

Table 1 shows the production conditions of the above Examples and Comparative Examples. In addition, the evaluation results and the measurement results are shown in Table 2.

Yes Carboxylic acid-containing polymers Additive polymer Inorganic Component Content (wt%) Monovalent ions Compound (B) Compound (A) Polyvalent metal ions Additive polymer Added amount (% by weight) Ion type Addition amount (mol%) Kinds Kinds Addition amount [mol% (*)] Ion type Neutralization Practical Example 1 PAA - - 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Ca ²⁺ 60 Example 2 PAA - - 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Mg ²⁺ 64 Example 3 PAA - - 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Zn ²⁺ 60 Example 4 PAA - - 30 - - TMOS a-1 10 Ca ²⁺ 63 Example 5 PAA - - 30 - - TMOS a-1 20 Ca ²⁺ 55 Example 6 PAA - - 8 - - - a-1 100 Ca ²⁺ 70 Example 7 PAA - - 20 - - TMOS a-1 10 Ca ²⁺ 67 Example 8 PAA - - 30 - - TMOS a-2 10 Ca ²⁺ 62 Example 9 PAA PVA 3 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Ca ²⁺ 58 Example 10 PAA Starch 3 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Ca ²⁺ 57 Example 11 PAA - - 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Ca ²⁺ 61 Example 12 PAA - - 30 - - TMOS a-1 10 Ca ²⁺ 5 Example 13 PAA - - 30 - - TMOS a-1 10 Ca ²⁺ 15 Comparative Example 1 PAA - - 30 - - TMOS a-1 10 - - Comparative Example 2 PAA - - 0 - - - - - Ca ²⁺ -

a-1: γ-glycidoxypropyltrimethoxysilane

a-2: γ-aminopropyltrimethoxysilane

(*) The ratio of compound (A) to the sum of compound (A) and compound (B) [(Compound (A)) / (Compound (A) + Compound (B))]

Yes Solution (S) viscosity increase rate (%) Oxygen permeability (cm ³ / m ² ㆍ day · atm) Oxygen permeability after retort treatment (cm ³ / m ² ㆍ day · atm) Surface appearance Falling turret breaking strength (times) Tensile strength and elongation 65% RH 85% RH 95% RH Strength (MPa) Elongation (%) Example 1 2 0.4 0.4 0.5 0.2> AA 115 140 220 Example 2 2 0.4 0.4 0.5 0.2> AA 117 140 200 Example 3 2 0.4 0.4 0.5 0.2> AA 110 130 220 Example 4 0 0.2 0.2 0.2 0.2> A 101 140 220 Example 5 0 0.5 0.5 0.6 0.2> AA 94 120 180 Example 6 0 0.2 0.2 0.2 0.2> AA 82 100 160 Example 7 0 0.4 0.4 0.5 0.2> AA 96 120 170 Example 8 One 0.8 0.8 1.0 0.2> A 98 140 200 Example 9 One 0.2 0.2 0.2 0.2> AA 134 160 240 Example 10 One 0.2 0.2 0.2 0.2> A 137 160 230 Example 11 2 0.7 0.7 0.8 0.2> A 98 130 190 Example 12 2 35 45 68 60 A 121 140 200 Example 13 2 11 13 25 12 A 110 160 210 Comparative Example 1 One 38 52 83 87 A 112 140 200 Comparative Example 2 - - - - - - - - -

As shown in Table 2, the laminates (B-1) to (B-13) of Examples 1 to 13 had higher oxygen barrier than the laminate 4 of Comparative Example 1, which was not subjected to ionization treatment under any conditions. Indicates the last name. Among these, the laminated body (B-1)-(B-11) of Example 1- Example 11 and Example 13, the laminated body (B-1)-(B-11) of 13, and laminated body (B-13) ), In particular, the laminates (B-1) to (B-11) of Examples 1 to 11 exhibit high oxygen barrier properties under any conditions without depending on humidity. In addition, these laminates are transparent and have a good surface appearance. Moreover, these laminated bodies show favorable characteristics without falling in tensile strength and elongation compared with the film of the OPET single layer in which the gas barrier layer is not formed.

In addition, as shown in Table 2, the laminates (B-1-1) to (B-13-1) of Examples 1 to 13 were oxygen even after the retort treatment compared with the laminate of Comparative Example 1. High blocking In particular, in the laminate of Examples 1 to 11 and Example 13 (among them, Examples 1 to 11), the oxygen barrier property after retort treatment is very high.

Further, the laminates (B-1-1) to (B-13-1) having a multilayer structure produced in Examples 1 to 13 had high drop bag breaking strength and good bend resistance.

In addition, as shown in Table 2, even if all of solution S1-S10 passed two days, a viscosity change is hardly confirmed.

<Example 14>

First, the solution S1 is produced in the same manner as in Example 1. Using this solution (S1), a gas barrier layer is formed on the substrate (OPET) by the following method.

Takerak A3210 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd. is used as a polyol-based motif of a two-component anchor coating agent, and Takeate A3072 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd. is used as an aromatic isocyanate-based curing agent. do. After mixing these main materials, the hardening | curing agent, and ethyl acetate (the water content in ethyl acetate is 340 ppm) so that the weight ratio of main / hardening agent may be 1/1, it is a stretched PET film [OPET; Made by Toray Industries, Ltd., Lumira (trade name)] and dried. Thus, the base material (AC / OPET) which has an anchor coating layer (adhesive layer) of thickness 0.1 micrometer is produced. The solution (S1) was coated on the anchor coating layer of this substrate so as to have a thickness of 1 탆 by a bar coater, and then dried at 80 ° C. for 5 minutes. Subsequently, the same two-component anchor coating agent is applied to the other side of the stretched PET film with the same thickness and dried. The solution (S1) is coated with a bar coater so that the thickness after drying is 1 µm on this anchor coating layer, and dried at 80 ° C. for 5 minutes. Subsequently, heat treatment was performed at 200 ° C. for 5 minutes in dry air, and the gas barrier layer (1 μm) / AC (0.1 μm) / OPET (12 μm) / AC (0.1 μm) / gas barrier layer (1 μm) A laminate 14 having a structure is obtained. The gas barrier layer is colorless and transparent and has a good appearance.

Next, the laminate 14 is subjected to ionization treatment using calcium acetate aqueous solution (MI-1) under the same conditions as in Example 1. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 占 폚, and then dried at 80 占 폚 for 5 minutes to obtain a laminate (B-14) of the present invention. About the laminated body (B-14), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 61 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, change in appearance with heating, tensile strength, elongation, haze, and inorganic component content of the laminate (B-14) were evaluated by the aforementioned method.

Moreover, the laminated body (B) which has a structure of gas barrier layer / AC / OPT / AC / gas barrier layer / adhesive agent / ONy / adhesive agent / PP by the method similar to Example 1 using laminated body B-14. -14-1). The drop bag breaking strength, the peeling strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree of the outermost layer after the retort treatment is 93 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.2 cm ³ / m ² · day · atm.

<Example 15>

Gas barrier layer (1 μm) / AC (0.2 μm) / OPET (12 μm) / AC (0.2 μm) / gas barrier layer in the same manner as in Example 14 except that the thickness of the anchor coating layer was 0.2 μm. The laminated body 15 which has a structure of (1 micrometer) is obtained. The gas barrier layer is colorless and transparent and has a good appearance.

Next, the laminate 15 is subjected to ionization treatment using calcium acetate aqueous solution (MI-1) under the same conditions as in Example 1. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 ° C., and then dried at 80 ° C. for 5 minutes to obtain a laminate (B-15) of the present invention. About the laminated body (B-15), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 61 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, change in appearance with heating, tensile strength, elongation, haze, and inorganic component content of the laminate (B-15) were evaluated by the above-described method.

In addition, using the laminated body B-15, the laminated body (B) which has a structure of gas barrier layer / AC / OPT / AC / gas barrier layer / adhesive / ONy / adhesive / PP in the same manner as in Example 1 -15-1). The drop bag breaking strength, the peeling strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree of the outermost layer after the retort treatment is 90 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.2 cm ³ / m ² · day · atm.

<Example 16>

Example 14 and the weight of the main component, the hardening agent, and ethyl acetate (the water content in ethyl acetate is 320 ppm) of the two-component anchor coating agent were 3/1 (topic / hardener). In the same manner, a laminate 16 having a structure of gas barrier layer (1 μm) / AC (0.1 μm) / OPET (12 μm) / AC (0.1 μm) / gas barrier layer (1 μm) was obtained. The gas barrier layer is colorless and transparent and has a good appearance.

Next, the laminate 16 is subjected to ionization treatment using calcium acetate aqueous solution (MI-1) under the same conditions as in Example 1. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 ° C., and then dried at 80 ° C. for 5 minutes to obtain a laminate (B-16) of the present invention. About the laminated body (B-16), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 61 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, appearance change with heating, tensile strength, elongation, haze, and inorganic component content of the laminate (B-16) were evaluated by the above-described method.

In addition, using the laminated body B-16, the laminated body (B) which has a structure of gas barrier layer / AC / OPT / AC / gas barrier layer / adhesive / ONy / adhesive / PP in the same manner as in Example 1 -16-1). The drop bag breaking strength, the peeling strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree of the outermost layer after the retort treatment is 90 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.2 cm ³ / m ² · day · atm.

<Example 17>

Example 14, except that the main component of the two-component anchor coating agent, the curing agent and ethyl acetate (the water content of ethyl acetate is 5000 ppm), and the weight ratio of the main agent and the curing agent to 1/1 (topic / hardener) In the same manner, a laminate 17 having a structure of a gas barrier layer (1 μm) / AC (0.1 μm) / OPET (12 μm) / AC (0.1 μm) / gas barrier layer (1 μm) was obtained. The gas barrier layer is colorless and transparent and has a good appearance.

Next, the laminated body 17 is ionized using calcium acetate aqueous solution (MI-1) on the conditions similar to Example 1. FIG. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 ° C., and then dried at 80 ° C. for 5 minutes to obtain a laminate (B-17) of the present invention. About the laminated body (B-17), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 61 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, peeling strength, surface appearance, appearance change with heating, tensile strength, elongation, haze, and inorganic component content of the laminate (B-17) were evaluated by the aforementioned method.

In addition, using the laminate (B-17), the laminate (B) having a structure of gas barrier layer / AC / OPET / AC / gas barrier layer / adhesive / ONy / adhesive / PP in the same manner as in Example 1 -17-1). The drop bag breaking strength, the peeling strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree of the outermost layer after the retort treatment is 90 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.2 cm ³ / m ² · day · atm.

Example 18

Structure of the gas barrier layer (1 μm) / AC (0.1 μm) / OPET (12 μm) / AC (0.1 μm) / gas barrier layer (1 μm) in the same manner as in Example 14, except that the anchor coating was different. A laminate 18 having is obtained. The gas barrier layer is colorless and transparent and has a good appearance. In Example 18, a two-part anchor coating agent using a polyol-based main body and an aliphatic isocyanate-based curing agent hardly affected by moisture in an organic solvent is used as the anchor coating agent. Takerak A626 (brand name) by Mitsudake Chemical Co., Ltd. is used for the subject, and Takeate A50 (brand name) by Mitsui Take Chemical Co., Ltd. is used for hardening agent. The main body, the curing agent, and ethyl acetate (the moisture contained in ethyl acetate is 1200 ppm) are mixed so that the weight ratio of the main body and the curing agent is 4/3 (topic / curing agent).

Next, the laminate 18 is subjected to ionization treatment using calcium acetate aqueous solution (MI-1) under the same conditions as in Example 1. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 占 폚, and then dried at 80 占 폚 for 5 minutes to obtain a laminate (B-18) of the present invention. About the laminated body (B-18), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 61 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, change in appearance with heating, tensile strength, elongation, haze, and inorganic component content of the laminate (B-18) were evaluated by the above-described method.

In addition, using the laminated body B-18, the laminated body (B) which has a structure of a gas barrier layer / AC / OPT / AC / gas barrier layer / adhesive / ONy / adhesive / PP in the same manner as in Example 1 -18-1). The drop bag breaking strength, the peeling strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree of the outermost layer after the retort treatment is 90 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.2 cm ³ / m ² · day · atm.

Example 19

First, the solution S1 is produced in the same manner as in Example 1.

As the anchor coating agent, a two-component anchor coating agent using an aliphatic isocyanate curing agent that is less susceptible to the influence of moisture in the polyol base and the organic solvent is applied. Takerak A626 (brand name) by Mitsudake Chemical Co., Ltd. is used for the subject, and Takeate A50 (brand name) by Mitsui Take Chemical Co., Ltd. is used for hardening agent. The main body, the curing agent, and ethyl acetate (the moisture contained in ethyl acetate is 560 ppm) are mixed so that the weight ratio of the main body and the curing agent is 4/3 (topic / curing agent), and the stretched PET film [OPET; Made by Toray Industries, Ltd., Lumira (trade name)] and dried. In this manner, a substrate (AC / OPET) having an anchor coating layer (adhesive layer) having a thickness of 0.1 μm is produced.

Subsequently, an aluminum oxide layer (thickness of 30 nm) is deposited on the anchor coating layer in the vacuum deposition apparatus using the electron beam heating method. Subsequently, the solution (S1) was coated with a bar coater so that the thickness after drying was 1 μm on the aluminum oxide layer, and then dried at 80 ° C. for 5 minutes, and then heat-treated at 200 ° C. for 5 minutes in dry air. In this way, a laminate 19 having a structure of a gas barrier layer (1 μm) / aluminum oxide layer / AC / OPET (12 μm) is obtained. The gas barrier layer is colorless and transparent and has a good appearance.

Next, the laminate 19 is subjected to ionization treatment using calcium acetate aqueous solution (MI-1) under the same conditions as in Example 1. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 占 폚, and then dried at 80 占 폚 for 5 minutes to obtain a laminate (B-19) of the present invention. About the laminated body (B-19), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 61 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, appearance change with heating, tensile strength, elongation, haze, and inorganic component content of the laminate (B-19) were evaluated by the above-described method.

In addition, the laminated body (B-19-) which has a structure of OPET / AC / deposited thin film layer / gas barrier layer / adhesive agent / ONy / adhesive agent / PP by the method similar to Example 1 using laminated body (B-19). 1) to make. The drop bag breaking strength, the peeling strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree of the outermost layer after the retort treatment is 90 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.2 cm ³ / m ² · day · atm.

Example 20

First, the solution S1 is produced in the same manner as in Example 1.

As the anchor coating agent, a two-part anchor coating agent using a polyol-based main material and an aliphatic isocyanate curing agent is applied. Takerak A626 (brand name) by Mitsudake Chemical Co., Ltd. is used for the subject, and Takeate A50 (brand name) by Mitsui Take Chemical Co., Ltd. is used for hardening agent. The main body, the curing agent, and ethyl acetate (the water content of ethyl acetate is 620 ppm) are mixed so that the weight ratio of the main body and the curing agent is 4/3 (topic / curing agent), and the stretched PET film [OPET; Made by Toray Industries, Ltd., Lumira (trade name)] and dried. Thus, the base material (AC / OPET) which has an anchor coating layer (adhesive layer) of thickness 0.1 micrometer is produced.

Subsequently, a silicon oxide layer (thickness of 25 nm) is deposited on the anchor coating layer in the vacuum deposition apparatus using the electron beam heating method. Subsequently, the solution (S1) was coated on the silicon oxide layer with a bar coater so that the thickness after drying was 1 μm, and then dried at 80 ° C. for 5 minutes, and then heat-treated at 200 ° C. for 5 minutes in dry air. In this way, a laminate 20 having a structure of a gas barrier layer (1 μm) / silicon oxide layer / AC / OPET (12 μm) is obtained. The gas barrier layer is colorless and transparent and has a good appearance.

Next, the laminate 20 is subjected to ionization treatment using calcium acetate aqueous solution (MI-1) under the same conditions as in Example 1. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 ° C., and then dried at 80 ° C. for 5 minutes to obtain a laminate (B-20) of the present invention. About the laminated body (B-20), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 60 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, appearance change with heating, tensile strength, elongation, haze, and inorganic component content of the laminate (B-20) were evaluated by the above-described method.

In addition, using the laminate (B-20), a laminate (B-) having a structure of OPET / AC / deposited thin film layer / gas barrier layer / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 1. To make. The drop bag breaking strength, the peeling strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree of the outermost layer after the retort treatment is 88 mol%, and the oxygen permeability after the retort treatment is very good, less than 0.2 cm ³ / m ² · day · atm.

Example 21

Gas barrier layer (1 μm) / AC (0.1 μm) / OPET (12 μm) / AC (0.1 μm) / in the same manner as in Example 14, except that the heat treatment was not performed at 200 ° C. for 5 minutes. The laminated body 21 which has a structure of a gas barrier layer (1 micrometer) is obtained. The gas barrier layer is colorless and transparent and has a good appearance.

Next, the laminated body 21 is ionized using calcium acetate aqueous solution (MI-1) on the conditions similar to Example 1. FIG. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 占 폚, and then dried at 80 占 폚 for 5 minutes to obtain a laminate (B-21) of the present invention. About the laminated body (B-21), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 94 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, appearance change with heating, tensile strength, elongation, haze, and inorganic component content of the laminate (B-21) were evaluated by the above-described method.

In addition, using the laminated body B-21, the laminated body (B) which has a structure of gas barrier layer / AC / OPT / AC / gas barrier layer / adhesive / ONy / adhesive / PP in the same manner as in Example 1 -21-1). The drop bag breaking strength, the peeling strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree of the outermost layer after the retort treatment is 96 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.3 cm ³ / m ² · day · atm. The oxygen permeability after the retort treatment using ion-exchanged water is 0.3 cm ³ / m ² · day · atm.

<Example 22>

First, in the same manner as in Example 14, a laminate having a structure of a gas barrier layer (1 μm) / AC (0.1 μm) / OPET (12 μm) / AC (0.1 μm) / gas barrier layer (1 μm) ( 22) is obtained. The gas barrier layer is colorless and transparent and has a good appearance.

Next, the ionization treatment is performed on the laminate 22 under the same conditions as in Example 1 except that the ionization treatment time is 300 seconds. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 DEG C, and then dried at 80 DEG C for 5 minutes to obtain a laminate (B-22) of the present invention. About the laminated body (B-22), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 97 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, appearance change with heating, tensile strength, elongation, haze, and inorganic component content of the laminate (B-22) were evaluated by the above-described method.

In addition, using the laminated body (B-22), the laminated body (B) which has a structure of a gas barrier layer / AC / OPT / AC / gas barrier layer / adhesive / ONy / adhesive / PP in the same manner as in Example 1 -22-1). The drop bag breaking strength, the peeling strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree of the outermost layer after the retort treatment is 93 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.2 cm ³ / m ² · day · atm. In addition, the retort treatment is performed with ion-exchanged water.

Comparative Example 3

In the same manner as in Example 14, a laminate having a structure of gas barrier layer (1 μm) / AC (0.1 μm) / OPET (12 μm) / AC (0.1 μm) / gas barrier layer (1 μm) was obtained. . The gas barrier layer is colorless and transparent and has a good appearance.

The obtained laminate was neutralized with an aqueous sodium acetate solution as described below. First, sodium acetate is dissolved in distilled water so that the concentration is 10% by weight, and this aqueous solution is kept at 80 ° C. The laminate is then immersed in this aqueous solution for about 20 seconds. After immersion, the laminate was taken out, the surface of the laminate was washed with distilled water adjusted to 80 캜, and then dried at 80 캜 for 5 minutes to obtain a laminate (C3). About the said laminated body (C3), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 63 mol% of the carboxyl groups were neutralized with sodium ions. The oxygen barrier property, surface appearance, tensile strength, elongation, and inorganic component content rate of the laminate (C3) thus obtained were evaluated by the above-described method.

In addition, the laminated body (C-3) which has a structure of gas barrier layer / AC / OPT / AC / gas barrier layer / adhesive agent / ONy / adhesive agent / PP by the method similar to Example 1 using laminated body C3. -1) to make. The drop bag breaking strength, the peeling strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree of the outermost layer after the retort treatment is 63 mol%, and the oxygen permeability after the retort treatment is 84 cm ³ / m ² · day · atm. In addition, in this comparative example, a retort process is performed using ion-exchange water.

Table 3 shows the production conditions of the above Examples 14 to 21 and Comparative Example 3. In addition, the evaluation results and the measurement results are shown in Table 4. In addition, the nitrogen content rate of an anchor coating agent is the value calculated | required from elemental analysis.

Yes Carboxylic acid-containing polymers AC layer Floor composition Inorganic Component Content (wt%) Monovalent ions Compound (B) Compound (A) Polyvalent metal ions Nitrogen content rate (% by weight) Thickness (㎛) Ion type Addition amount (mol%) Kinds Kinds Addition amount [mol% (*)] Ion type Neutralization Example 14 PAA 7.9 0.1 both sides 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Ca ²⁺ 61 Example 15 PAA 7.9 0.2 both sides 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Ca ²⁺ 61 Example 16 PAA 4.4 0.1 both sides 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Ca ²⁺ 61 Example 17 PAA 7.2 0.1 both sides 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Ca ²⁺ 61 Example 18 PAA 4.9 0.1 both sides 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Ca ²⁺ 61 Example 19 PAA 4.9 0.1 section 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Ca ²⁺ 61 Example 20 PAA 4.9 0.1 section 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Ca ²⁺ 60 Example 21 PAA 7.2 0.1 both sides 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Ca ²⁺ 94 Example 22 PAA 7.2 0.1 both sides 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Ca ²⁺ 97 Comparative Example 3 PAA 7.2 0.1 both sides 30 NH ₄ ⁺ 1.5 TMOS a-1 10 (Na ⁺ ) (63)

a-1: γ-glycidoxypropyltrimethoxysilane

(*): Ratio of compound (A) to the sum of compound (A) and compound (B) [(compound (A)) / (compound (A) + compound (B))]

Yes Solution (S) viscosity increase rate (%) Oxygen permeability (cm ³ / m ² ㆍ day · atm) Oxygen permeability after retort treatment (cm ³ / m ² ㆍ day · atm) 3σ of haze Surface appearance Surface appearance after heating Peel Strength [g / 15mm] Falling turret breaking strength (times) Tensile strength and elongation 65% RH 85% RH 95% RH Strength (MPa) Elongation (%) Example 14 2 0.4 0.4 0.5 0.2> 0.63 AA AA 570 120 140 210 Example 15 2 0.4 0.4 0.5 0.2> 0.60 AA B 630 130 130 180 Example 16 2 0.4 0.4 0.5 0.2> 0.60 AA A 550 110 130 220 Example 17 2 0.4 0.4 0.5 0.2> 2.40 A A 250 78 140 220 Example 18 2 0.4 0.4 0.5 0.2> 0.30 AA AA 560 125 120 190 Example 19 2 0.2> 0.2> 0.2> 0.2> 0.30 AA AA 380 73 120 200 Example 20 2 0.2> 0.2> 0.2> 0.2> 0.30 AA AA 360 81 110 200 Example 21 2 0.2> 0.2> 0.2> 0.2> 0.60 AA B 570 52 120 220 Example 22 2 0.2> 0.2> 0.2> 0.2> 0.62 AA AA 600 118 140 200 Comparative Example 3 2 84 87 89 87 0.59 AA AA 590 110 140 190

<Example 23>

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water, and then ammonia water was added to neutralize 1.5 mol% of the carboxyl group of polyacrylic acid, thereby obtaining an aqueous polyacrylic acid solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 68.4 parts by weight of tetramethoxysilane (TMOS) was dissolved in 79.8 parts by weight of methanol, and then 11.4 parts by weight of 3-chloropropyltrimethoxysilane (manufactured by Chisso Corp.) was dissolved, followed by 5.13 parts by weight of distilled water. 12.7 parts by weight of 0.1 N hydrochloric acid is added to prepare a sol, which is subjected to hydrolysis and condensation at 1O &lt; 0 &gt; C for 1 hour with stirring. The obtained sol was diluted in 189 parts by weight of distilled water, and then rapidly added to 657 parts by weight of a 10% by weight aqueous solution of polyacrylic acid under stirring to obtain a solution (S23).

On the other hand, a base material having an anchor coating layer by coating a two-component anchor coating agent (manufactured by Mitsui Takeda Chemical Co., Ltd .: Takerak 3210 (trade name) and Takenate A3072 (trade name)) on a stretched PET film (OPET) and drying it AC / OPET). After coating the solution (S23) with a bar coater so that the thickness after drying on the anchor coating layer of this substrate to 2㎛, it is dried for 5 minutes at 80 ℃, heat treatment for 5 minutes at 200 ℃ in dry air. In this way, a laminate 23 having a structure of a gas barrier layer (2 μm) / AC / OPET (12 μm) is obtained. This gas barrier layer is colorless and transparent and has a very good appearance.

Then, calcium acetate is dissolved in distilled water so that the concentration is 10% by weight, and this aqueous solution is kept at 80 ° C. And the laminated body 23 is immersed for about 5 second in this aqueous solution (80 degreeC; MI-1). After immersion, the laminate was taken out, the surface of the laminate was washed with distilled water adjusted to 80 占 폚 and then dried at 80 占 폚 for 5 seconds to obtain the laminate (B-23) of the present invention. About the said laminated body (B-23), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 69 mol% of the carboxyl groups were neutralized with calcium ions. The oxygen barrier property, haze, and inorganic component content rate of the laminated body (B-23) thus obtained are evaluated by the above-described method.

Further, stretched nylon film (manufactured by UNITIKA, Inc., brand name), thickness 15 µm, may be abbreviated as ONy, and polypropylene film [RXC-18 (trade name), manufactured by Tocelo Corporation, 50 micrometers in thickness, may be abbreviated PP below] The dried thing was prepared by coating a two-component adhesive [A385 (trade name) and A-50 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.), respectively, on the laminate. Laminate with (B-22; gas barrier layer / AC / OPET). In this way, a laminate (B-23-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP is obtained. Using this laminate, the neutralization degree after the retort treatment and the oxygen permeability after the retort treatment were measured. The neutralization degree after the retort treatment was 92 mol%, and the oxygen permeability after the retort treatment was very good at less than 0.2 cm ³ / m ² · day · atm.

<Example 24>

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water, and then ammonia water was added to neutralize 1.5 mol% of the carboxyl group of polyacrylic acid, thereby obtaining an aqueous polyacrylic acid solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 68.4 parts by weight of tetramethoxysilane was dissolved in 79.7 parts by weight of methanol, and then 11.3 parts by weight of 3-mercaptopropyltrimethoxysilane (manufactured by Chisso Corp.) was dissolved, followed by 5.13 parts by weight of distilled water and 0.1 N. 12.7 parts by weight of hydrochloric acid was added to prepare a sol, which was then subjected to hydrolysis and condensation at 10 ° C. for 1 hour while stirring. The obtained sol was diluted in 189 parts by weight of distilled water and then rapidly added to 658 parts by weight of an aqueous 10% by weight polyacrylic acid solution under stirring to obtain a solution (S24). The storage stability is evaluated by the above-described method for this solution (S24).

Subsequently, a laminate 24 having a structure of a gas barrier layer (2 μm) / AC / OPET (12 μm) in the same manner as in Example 23, except that the solution S24 was used instead of the solution S23. ). In the laminate 24, the gas barrier layer is colorless and transparent, and the surface appearance is very good.

Next, the laminated body 24 is ionized using calcium acetate aqueous solution (MI-1) on the conditions similar to Example 23. FIG. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 占 폚, and then dried at 80 占 폚 for 5 minutes to obtain a laminate (B-24) of the present invention. About the laminated body (B-24), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 86 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, haze, and an inorganic component content rate of a laminated body (B-24) are evaluated by said method.

In addition, using the laminate (B-24), a laminate (B-24-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 23. To make. About this laminated body, the neutralization degree after a retort process and the oxygen permeability after a retort process are measured. The neutralization degree after the retort treatment was 95 mol%, and the oxygen permeability after the retort treatment was very good at less than 0.2 cm ³ / m ² · day · atm.

<Example 25>

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water, and then ammonia water was added to neutralize 1.5 mol% of the carboxyl group of polyacrylic acid, thereby obtaining an aqueous polyacrylic acid solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 68.4 parts by weight of tetramethoxysilane was dissolved in 68.4 parts by weight of methanol, and then 23.0 parts by weight of a 50% ethanol solution of N- (3-triethoxysilylpropyl) gluconamide (sales: Chisso Corp.) was added. After dissolving, 5.13 parts by weight of distilled water and 12.7 parts by weight of 0.1 N hydrochloric acid were added to prepare a sol, which was subjected to hydrolysis and condensation reaction at 10 ° C. for 1 hour while stirring. The obtained sol was diluted in 189 parts by weight of distilled water, and then rapidly added to 541 parts by weight of a 10% by weight aqueous solution of polyacrylic acid under stirring to obtain a solution (S25). The storage stability is evaluated by the above-described method for this solution (S25).

Subsequently, the laminate 25 having a structure of a gas barrier layer (2 μm) / AC / OPET (12 μm) in the same manner as in Example 23, except that the solution S25 was used instead of the solution S23. ). In the laminate 25, the gas barrier layer is colorless and transparent, and the appearance of the surface is very good.

Next, the laminated body 25 is ionized using calcium acetate aqueous solution (MI-1) on the conditions similar to Example 23. FIG. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 占 폚, and then dried at 80 占 폚 for 5 minutes to obtain a laminate (B-25) of the present invention. About the laminated body (B-25), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 50 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, the haze, and the inorganic component content rate of the laminated body (B-25) are evaluated by the above-mentioned method.

Moreover, using the laminated body B-25, the laminated body B-25-1 which has a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was carried out in the same manner as in Example 23. To make. About this laminated body, the neutralization degree after a retort process and the oxygen permeability after a retort process are measured. The neutralization degree after the retort treatment was 89 mol%, and the oxygen permeability after the retort treatment was very good at less than 0.2 cm ³ / m ² · day · atm.

Example 26

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water, and then ammonia water was added to neutralize 1.5 mol% of the carboxyl group of polyacrylic acid, thereby obtaining an aqueous polyacrylic acid solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 60.8 parts by weight of tetramethoxysilane was dissolved in 83.6 parts by weight of methanol, followed by dissolving 22.9 parts by weight of 3-chloropropyltrimethoxysilane, and then 5.20 parts by weight of distilled water and 12.9 parts by weight of 0.1N hydrochloric acid were added to prepare a sol. The mixture is subjected to hydrolysis and condensation reaction at 10 ° C. for 1 hour with stirring. The obtained sol was diluted in 247 parts by weight of distilled water and then rapidly added to 567 parts by weight of a 10% by weight aqueous solution of polyacrylic acid under stirring to obtain a solution (S26). The storage stability is evaluated by the above-described method for this solution (S26).

Subsequently, a laminate 26 having a structure of a gas barrier layer (2 μm) / AC / OPET (12 μm) in the same manner as in Example 23, except that solution S26 was used instead of solution S23. ). In the laminate 26, the gas barrier layer is colorless and transparent, and the appearance of the surface is very good.

Next, the laminated body 26 is ionized using calcium acetate aqueous solution (MI-1) on the conditions similar to Example 23. FIG. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 占 폚, and then dried at 80 占 폚 for 5 minutes to obtain a laminate (B-26) of the present invention. About the laminated body (B-26), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 55 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, haze, and an inorganic component content rate of a laminated body (B-26) are evaluated by the above-mentioned method.

Further, using the laminate (B-26), a laminate (B-26-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 23. To make. About this laminated body, the neutralization degree after a retort process and the oxygen permeability after a retort process are measured. The neutralization degree after the retort treatment was 74 mol%, and the oxygen permeability after the retort treatment was very good at less than 0.2 cm ³ / m ² · day · atm.

Example 27

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 is dissolved in distilled water to obtain a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 68.4 parts by weight of tetramethoxysilane was dissolved in 79.8 parts by weight of methanol, and then 11.4 parts by weight of 3-chloropropyltrimethoxysilane was dissolved, and then 5.13 parts by weight of distilled water and 12.7 parts by weight of 0.1N hydrochloric acid were added to prepare a sol. The mixture is subjected to hydrolysis and condensation reaction at 10 ° C. for 1 hour with stirring. The obtained sol was diluted in 189 parts by weight of distilled water and then rapidly added to 657 parts by weight of a 10% by weight aqueous solution of polyacrylic acid under stirring to obtain a solution (S27). The storage stability is evaluated by the above-described method for this solution (S27).

Subsequently, the laminate 27 having a structure of a gas barrier layer (2 μm) / AC / OPET (12 μm) in the same manner as in Example 23, except that the solution S27 was used instead of the solution S23. ). In the laminate 27, the gas barrier layer is colorless and transparent, and the surface appearance is very good.

Next, the laminated body 27 is ionized using calcium acetate aqueous solution (MI-1) on the conditions similar to Example 23. FIG. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 占 폚, and then dried at 80 占 폚 for 5 minutes to obtain a laminate (B-27) of the present invention. About the laminated body (B-27), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 69 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, haze, and an inorganic component content rate of a laminated body (B-27) are evaluated by the above-mentioned method.

In addition, using the laminate (B-27), a laminate (B-27-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 23. To make. About this laminated body, the neutralization degree after a retort process and the oxygen permeability after a retort process are measured. The neutralization degree after the retort treatment was 91 mol%, and the oxygen permeability after the retort treatment was very good at less than 0.2 cm ³ / m ² · day · atm.

<Example 28>

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 is dissolved in distilled water to obtain a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 68.4 parts by weight of tetramethoxysilane was dissolved in 79.7 parts by weight of methanol, followed by dissolving 11.3 parts by weight of 3-mercaptopropyltrimethoxysilane, and then 5.13 parts by weight of distilled water and 12.7 parts by weight of 0.1N hydrochloric acid were added to the sol. To prepare a hydrolysis and condensation reaction at 10 ℃ for 1 hour while stirring. The obtained sol was diluted in 189 parts by weight of distilled water and then rapidly added to 658 parts by weight of an aqueous 10% by weight polyacrylic acid solution under stirring to obtain a solution S28. The storage stability is evaluated by the method described above for this solution (S28).

Subsequently, a laminate 28 having a structure of a gas barrier layer (2 μm) / AC / OPET (12 μm) in the same manner as in Example 23, except that the solution S28 was used instead of the solution S23. ). In the laminate 28, the gas barrier layer is colorless and transparent, and the appearance of the surface is very good.

The obtained laminate 28 was subjected to ionization treatment using calcium acetate aqueous solution (MI-1) under the same conditions as in Example 23. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 占 폚, and then dried at 80 占 폚 for 5 minutes to obtain a laminate (B-6) of the present invention. About the laminated body (B-28), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 85 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, haze, and an inorganic component content rate of a laminated body (B-28) are evaluated by the above-mentioned method.

Further, using the laminate (B-28), a laminate (B-28-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 23. To make. About this laminated body, the neutralization degree after a retort process and the oxygen permeability after a retort process are measured. The neutralization degree after the retort treatment was 90 mol%, and the oxygen permeability after the retort treatment was very good at less than 0.2 cm ³ / m ² · day · atm.

<Example 29>

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 is dissolved in distilled water to obtain a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 68.4 parts by weight of tetramethoxysilane was dissolved in 82.0 parts by weight of methanol, followed by dissolving 13.6 parts by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by Chisso Corp.), followed by 5.13 parts by weight of distilled water and 0.1 12.7 parts by weight of N hydrochloric acid is added to prepare a sol, which is subjected to hydrolysis and condensation at 1O &lt; 0 &gt; C with stirring. The obtained sol was diluted in 185 parts by weight of distilled water and then rapidly added to 634 parts by weight of an aqueous 10% by weight polyacrylic acid solution under stirring to obtain a solution (S29). The storage stability is evaluated by the above-described method for this solution (S29).

Subsequently, the laminate 29 having a structure of a gas barrier layer (2 μm) / AC / OPET (12 μm) in the same manner as in Example 23, except that the solution S29 was used instead of the solution S23. ). In the laminate 29, the gas barrier layer is colorless and transparent and has a good appearance.

Next, the laminated body 29 is ionized using calcium acetate aqueous solution (MI-1) on the conditions similar to Example 23. FIG. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 DEG C, and then dried at 80 DEG C for 5 minutes to obtain a laminate (B-29) of the present invention. About the laminated body (B-29), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 63 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, haze, and an inorganic component content rate of a laminated body (B-29) are evaluated by the above-mentioned method.

In addition, using the laminate (B-29), a laminate (B-29-1) having a structure of gas barrier layer / AC / OPET / adhesive / ONy / adhesive / PP was prepared in the same manner as in Example 23. To make. The drop bag breaking strength, the neutralization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The neutralization degree after the retort treatment was 92 mol%, and the oxygen permeability after the retort treatment was very good at less than 0.2 cm ³ / m ² · day · atm.

<Example 30>

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water, and then ammonia water was added to neutralize 1.5 mol% of the carboxyl group of polyacrylic acid, thereby obtaining an aqueous polyacrylic acid solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 84.2 parts by weight of tetramethoxysilane (TMOS) was dissolved in 90.8 parts by weight of methanol, followed by dissolving 6.60 parts by weight of 3-mercaptopropyltrimethoxysilane, followed by 5.93 parts by weight of distilled water and 14.7 parts by weight of 0.1N hydrochloric acid. It is added to prepare a sol, it is subjected to hydrolysis and condensation reaction at 10 ℃ for 1 hour while stirring. The obtained sol was diluted in 173 parts by weight of distilled water, and then rapidly added to 625 parts by weight of a 10% by weight aqueous solution of polyacrylic acid under stirring to obtain a solution (S30). The storage stability is evaluated by the above-described method for this solution (S30).

Structure of the gas barrier layer (1 μm) / AC (0.1 μm) / OPET (12 μm) / AC (0.1 μm) / gas barrier layer (1 μm) in the same manner as in Example 14, except that the anchor coating was different. A laminate 30 having is obtained. The gas barrier layer is colorless and transparent and has a good appearance. In Example 30, a two-part anchor coating agent using a polyol-based main body and an aliphatic isocyanate curing agent is applied as the anchor coating agent. Takerak A626 (brand name) by Mitsudake Chemical Co., Ltd. is used for the subject, and Takeate A50 (brand name) by Mitsui Take Chemical Co., Ltd. is used for hardening agent. The main body, the curing agent, and ethyl acetate (the moisture contained in ethyl acetate is 520 ppm) are mixed so that the weight ratio of the main body and the curing agent is 4/3 (topic / curing agent).

Next, the laminated body 30 is ionized using calcium acetate aqueous solution (MI-1) on the conditions similar to Example 1. FIG. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 ° C., and then dried at 80 ° C. for 5 minutes to obtain a laminate (B-30) of the present invention. About the laminated body (B-30), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 97 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, appearance change with heating, tensile strength, elongation, haze, and inorganic component content rate of the laminated body (B-30) are evaluated by the above-mentioned method.

In addition, the laminated body (B) which has a structure of gas barrier layer / AC / OPT / AC / gas barrier layer / adhesive / ONy / adhesive / PP by the same method as Example 1 using laminated body B-30. -30-1). The drop bag breaking strength, the peeling strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree of the outermost layer after the retort treatment is 98 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.2 cm ³ / m ² · day · atm.

<Example 31>

Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water, and then ammonia water was added to neutralize 1.5 mol% of the carboxyl group of polyacrylic acid, thereby obtaining an aqueous polyacrylic acid solution having a solid content concentration of 10% by weight in an aqueous solution.

Subsequently, 84.2 parts by weight of tetramethoxysilane (TMOS) was dissolved in 91.1 parts by weight of methanol, followed by dissolving 6.90 parts by weight of γ-isocyanatepropyltrimethoxysilane, followed by addition of 5.93 parts by weight of distilled water and 14.7 parts by weight of 0.1N hydrochloric acid. A sol is prepared and subjected to hydrolysis and condensation reaction at 10 ° C. for 1 hour with stirring. The obtained sol was diluted in 176 parts by weight of distilled water, and then rapidly added to 622 parts by weight of a 10% by weight aqueous solution of polyacrylic acid under stirring to obtain a solution (S31). The storage stability is evaluated by the above-described method for this solution (S31).

Structure of the gas barrier layer (1 μm) / AC (0.1 μm) / OPET (12 μm) / AC (0.1 μm) / gas barrier layer (1 μm) in the same manner as in Example 14, except that the anchor coating was different. A laminate 31 having is obtained. The gas barrier layer is colorless and transparent and has a good appearance. In Example 31, a two-part anchor coating agent using a polyol-based main body and an aliphatic isocyanate curing agent is applied as the anchor coating agent. Takerak A626 (brand name) by Mitsudake Chemical Co., Ltd. is used for the subject, and Takeate A50 (brand name) by Mitsui Take Chemical Co., Ltd. is used for hardening agent. The main body, the curing agent, and ethyl acetate (the moisture contained in ethyl acetate is 520 ppm) are mixed so that the weight ratio of the main body and the curing agent is 4/3 (topic / curing agent).

Next, the laminate 31 is subjected to ionization treatment using calcium acetate aqueous solution (MI-1) under the same conditions as in Example 1. Subsequently, excess calcium acetate is removed by washing with distilled water adjusted to 80 DEG C, and then dried at 80 DEG C for 5 minutes to obtain a laminate (B-31) of the present invention. About the laminated body (B-31), the neutralization degree of the carboxyl group of polyacrylic acid in a gas barrier layer is measured in accordance with the above-mentioned method. As a result, it was found that 82 mol% of the carboxyl groups were neutralized with calcium ions. In addition, the oxygen barrier property, surface appearance, appearance change with heating, tensile strength, elongation, haze, and inorganic content of the laminate (B-31) were evaluated by the above-described method.

In addition, using the laminated body (B-31), the laminated body (B) which has a structure of gas barrier layer / AC / OPT / AC / gas barrier layer / adhesive / ONy / adhesive / PP in the same manner as in Example 1 -30-1). The drop bag breaking strength, the peeling strength, the ionization degree after the retort treatment, and the oxygen permeability after the retort treatment were measured for the laminate. The ionization degree of the outermost layer after the retort treatment is 97 mol%, and the oxygen permeability after the retort treatment is very good at less than 0.2 cm ³ / m ² · day · atm.

Table 5 and Table 6 show the production conditions and evaluation results of the above examples.

Yes Carboxylic acid-containing polymers Inorganic Component Content (wt%) Monovalent ions Compound (B) Compound (A · A ') Polyvalent metal ions Ion type Addition amount (mol%) Kinds Kinds Addition amount [mol%] (*) Ion type Neutralization Example 23 PAA 30 NH ₄ ⁺ 1.5 TMOS a-1 10 Ca ²⁺ 69 Example 24 PAA 30 NH ₄ ⁺ 1.5 TMOS a-2 10 Ca ²⁺ 86 Example 25 PAA 30 NH ₄ ⁺ 1.5 TMOS a-3 10 Ca ²⁺ 50 Example 26 PAA 30 NH ₄ ⁺ 1.5 TMOS a-1 20 Ca ²⁺ 55 Example 27 PAA 30 - - TMOS a-1 10 Ca ²⁺ 69 Example 28 PAA 30 - - TMOS a-2 10 Ca ²⁺ 85 Example 29 PAA 30 - - TMOS b-1 10 Ca ²⁺ 63 Example 30 PAA 35 NH ₄ ⁺ 1.5 TMOS a-2 5 Ca ²⁺ 97 Example 31 PAA 35 NH ₄ ⁺ 1.5 TMOS b-2 5 Ca ²⁺ 82

a-1: 3-chloropropyltrimethoxysilane

a-2: 3-mercaptopropyl trimethoxysilane

a-3: N- (3-triethoxysilylpropyl) gluconamide

b-1: γ-glycidoxypropyltrimethoxysilane

b-2: γ-isocyanatepropyltrimethoxysilane

(*) Ratio of compound (A or A ') to the sum of compound (A or A') and compound (B) [(compound (A or A ')) / (compound (A or A') + compound ( B))]

Yes Stability of Solution (S) Haze (%) Oxygen permeability (cm ³ / m ² ㆍ day · atm) Before retort treatment After retort treatment Example 23 4 days 1.5 0.2 0.2> Example 24 4 days 1.8 0.3 0.2> Example 25 4 days 2.0 0.5 0.2> Example 26 4 days 1.2 0.5 0.2> Example 27 7 days or more 2.0 0.2 0.2> Example 28 7 days or more 2.4 0.3 0.2> Example 29 7 days or more 4.8 0.2 0.2> Example 30 4 days 2.2 0.2 0.2> Example 31 4 days 4.7 0.2 0.2>

As shown in Table 6, the laminates (B-23) to (B-31) of Examples 23 to 31 exhibit high oxygen barrier properties even under high humidity conditions. Further, the laminates (B-23) to (B28) and (B-30) have a haze value of 3% or less, which are small and transparent, and have a good surface appearance.

In addition, as shown in Table 6, the laminates (B-23-1) to (B-31-1) of Examples 23 to 31 have high oxygen barrier properties even after the retort treatment.

In addition, as shown in Table 6, all of the solutions (S23) to (S29) do not gel even after two days pass, and the coating property is also good.

As mentioned above, although embodiment of this invention was mentioned and demonstrated, the present invention is not limited to the said embodiment, It can apply to another embodiment based on the technical idea of this invention.

The present invention can be applied to a laminate requiring gas barrier properties and a method of manufacturing the same. In particular, the gas barrier layered product of the present invention exhibits high oxygen barrier properties regardless of humidity, and also exhibits high oxygen barrier properties even after retort treatment. Therefore, the gas barrier layered product of the present invention is effectively used as a packaging material for food, medicine, medical equipment, machine parts, clothing, and the like, and is particularly effectively used for food packaging applications requiring gas barrier properties under high humidity.

Claims (30)

A gas barrier laminate comprising a substrate and a layer laminated on at least one side of the substrate, The layer contains at least one functional group selected from a carboxyl group and a carboxylic anhydride group, and a hydrolyzed condensate of at least one compound (L) containing a metal atom bound to at least one characteristic group selected from a halogen atom and an alkoxy group. It consists of a composition containing the neutralization of the polymer At least a part of the -COO- group contained in at least one functional group is neutralized with a divalent or higher metal ion. The gas barrier layered product according to claim 1, wherein at least 10 mol% of -COO- groups contained in at least one functional group are neutralized with metal ions. The gas barrier layered product according to claim 1, wherein 0.1 to 10 mol% of -COO- groups contained in at least one functional group are neutralized with monovalent ions. The gas barrier layered product according to claim 1, wherein compound (L) contains at least one compound of formula (I). Formula I

In Formula I above, M ¹ is Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La or Nd, R ¹ is an alkyl group, X ¹ is a halogen atom, Z ¹ is an alkyl group substituted with a functional group having reactivity with a carboxyl group, m is equal to the valence of M ¹ , n is an integer from 0 to (m-1), k is an integer from 0 to (m-1), 1 ≦ n + k ≦ (m−1). The gas barrier layered product according to claim 4, wherein the functional group having a reactivity with a carboxyl group in formula (I) is at least one selected from an epoxy group, an amino group and an isocyanate group. The compound (L) according to claim 4, wherein the compound (L) consists of compound (A) and at least one compound (B) of the following formula (II), wherein the molar ratio of compound (A) / compound (B) is from 0.5 / 99.5 to 40/60 Range of gas barrier laminates. Formula II

In Formula II above, M ² is Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La or Nd, R ² is an alkyl group, R ³ is an alkyl group, an aralkyl group, an aryl group or an alkenyl group, X ² is a halogen atom, p is equivalent to the valence of M ² , q is an integer from 0 to p, r is an integer from 0 to p, 1 ≦ q + r ≦ p. The gas barrier layered product according to claim 1, wherein an organic group having at least one characteristic group selected from a halogen atom, a mercapto group and a hydroxyl group is further bonded to a metal atom of the compound (L). The gas barrier layered product according to claim 7, wherein the metal atom is a silicon atom. 8. A gas barrier layered product according to claim 7, wherein compound (L) contains at least one compound of formula (I '). Formula I '

In Formula I 'above, R ¹ and R ⁴ are each independently an alkyl group, X ¹ is a halogen atom, Z ² is an organic group having at least one characteristic group selected from a halogen atom, a mercapto group and a hydroxyl group, s is an integer from 0 to 3, t is an integer from 0 to 2, u is an integer from 0 to 3, 1 ≤ s + u ≤ 3, 1 ≦ s + t + u ≦ 3. The compound (L) according to claim 7, wherein the compound (L) is chloromethyltrialkoxysilane, chloromethyltrichlorosilane, 2-chloroethyltrialkoxysilane, 2-chloroethyltrichlorosilane, 3-chloropropytrialkoxysilane, 3- Chloropropyltrichlorosilane, mercaptomethyltrialkoxysilane, mercaptomethyltrichlorosilane, 2-mercaptoethyltrialkoxysilane, 2-mercaptoethyltrichlorosilane, 3-mercaptopropyltrialkoxysilane, 3-mer Gas barrier laminate comprising one or more compounds selected from captopropyltrichlorosilane, N- (3-trialkoxysilylpropyl) gluconamide, N- (3-trialkoxysilylpropyl) -4-hydroxybutylamide . The gas barrier layered product according to claim 7, wherein the oxygen permeation rate is 20 cm ³ / m ² · day · atm or less in an atmosphere of 85% RH. The gas barrier layered product according to claim 7, wherein the haze value is 3% or less. The gas barrier layered product according to claim 9, wherein the compound (L) further contains at least one compound (B) of the following formula (II). Formula II

In Formula II above, M ² is Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La or Nd, R ² is an alkyl group, R ³ is an alkyl group, an aralkyl group, an aryl group or an alkenyl group, X ² is a halogen atom, p is equivalent to the valence of M ² , q is an integer from 0 to p, r is an integer from 0 to p, 1 ≦ q + r ≦ p. The gas barrier layered product according to claim 13, wherein the molar ratio of Compound (A ') / Compound (B) is 0.1 / 99.9 to 40/60. The gas barrier layered product according to claim 1, wherein the content of the inorganic component contained in the composition is 5 to 50% by weight. The gas barrier layered product according to claim 1, wherein the polymer is at least one polymer selected from polyacrylic acid and polymethacrylic acid. The gas barrier layered product according to claim 1, wherein the metal ions are at least one ion selected from calcium ions, magnesium ions, barium ions and zinc ions. The gas barrier layered product according to claim 1, wherein the composition further contains polyalcohols. The gas barrier layered product according to claim 18, wherein the weight ratio of the neutralized / polyalcohols is 10/90 to 99.5 / 0.5. The gas barrier layered product according to claim 1, further comprising an adhesive layer disposed between the substrate and the layer. The gas barrier layered product according to claim 1, wherein the substrate comprises a paper layer. A package using the gas barrier laminate according to claim 1. The package according to claim 22, wherein the substrate included in the gas barrier layered product comprises a paper layer. A composition containing a hydrolysis condensate of at least one compound (L) containing a metal atom bonded to at least one characteristic group selected from a halogen atom and an alkoxy group, and a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group. A first step of forming a layer made of a substrate and And a second step of bringing the layer into contact with a solution containing bivalent or more metal ions. The method for producing a gas barrier laminate according to claim 24, wherein an organic group having at least one characteristic group selected from a halogen atom, a mercapto group, and a hydroxyl group is further bonded to a metal atom of the compound (L). The method for producing a gas barrier laminate according to claim 24, wherein at least 10 mol% of -COO- groups contained in at least one functional group are neutralized with divalent or higher metal ions in the second step. The compound according to claim 24, wherein the compound (L), the partial hydrolyzate of the compound (L), the complete hydrolyzate of the compound (L), the partial hydrolysis condensate of the compound (L) and the part of the complete hydrolyzate of the compound (L) Preparing a solution (S) containing at least one metal element-containing compound and polymer selected from those condensed, and The manufacturing method of the gas barrier layered product containing the process of forming a layer by apply | coating solution (S) to a base material and drying. The method according to claim 24, wherein the first step comprises the steps of forming a hydrolysis condensate, a step of preparing a solution S containing a hydrolysis condensate and a polymer, and applying the solution S to a substrate and drying the same. A method for producing a gas barrier laminate, comprising the step of forming a layer. The method for producing a gas barrier laminate according to claim 24, wherein in the polymer in solution (S), 0.1 to 10 mol% of the -COO- groups contained in one or more functional groups are neutralized by monovalent ions. The method of manufacturing a gas barrier laminate according to claim 24, further comprising a step of heat-treating the layer at a temperature of 120 to 240 ° C after the first process and before and / or after the second process.